Agent for reducing substrate dependence

ABSTRACT

The present invention relates to an agent for reducing substrate dependence useful as an ingredient of a resist composition used for preparation of semiconductor devices and the like, which comprises a compound shown by the following general formula [1]:                    
     wherein R 41  is a hydrogen atom or a methyl group, R 42  is a hydrogen atom, a methyl group, an ethyl group or a phenyl group, R 43  is a straight chained, branched or cyclic alkyl group having 1 to 6 carbon atoms, and n is 0 or 1.

BACKGROUND OF THE INVENTION

The present invention relates to a compound useful as an ingredient of aresist composition used for preparation of semiconductor elements andthe like, which can reduce substrate dependence of the resistcomposition, and to a resist composition in which the compound isincorporated.

In compliance with the requirement for ultra-fine processing accordingto high integration of semiconductor devices, the light source ofexposure used in lithography processes has recently been changed fromi-line (365 nm) to one having shorter wavelength such as KrF excimerlaser (248 nm), ArF excimer laser (193 nm) or electron beam. Inaccordance with the change from high-pressure mercury lump to excimerlaser as the exposure source, the resist composition to be used isrequired to be high sensitive and thus so-far useddissolution-inhibiting resist has been replaced by achemically-amplified resist composition. In chemically-amplified resistcompositions, an action of an acid generated by actinic radiation takesan important role, and therefore influence by the kind of the substrateis often observed, which has not been come into matter indissolution-inhibiting resist compositions. Namely, in a case of aspecial substrate such as SiN, TiN, SiON, BPSG and a strong basicorganic anti-reflective film, a basic substance and water generated fromthose substrate inactivate the generated acid on their surface, andconsequently no good pattern can be obtained. For this reason, thissubstrate dependence has been a serious problem in production ofsemiconductor, devices. In order to dissolve this problem inchemically-amplified resist compositions, there have been proposed useof an organic carboxylic acid such as salicylic acid (e.g. JapanesePatent Publication-Kokai-No. 262721/1996, No. 160247/1997), use of anorganic carboxylic acid such as diphenolic acid (e.g. Japanese PatentPublication-Kokia-No. 207066/1998, No. 20504/1998) or an imide compoundssuch as succinimide (e.g. Japanese Patent Publication-Kokai-No.44950/1999) and the like. However, addition of salicylic acid, etc.causes a problem concerning stability of a resist solution, and additionof diphenolic acid causes such a problem that almost no reduction ofsubstrate dependence is attained. Further, addition of succinimide, etc.can attain reduction of substrate dependence on some kind of substratesbut the reduction is still not enough. Such being the circumstances, ithas strongly been desired to develop such chemically-amplified resistcomposition as capable of forming a rectangular pattern even on aspecific substrate just like on an ordinary substrate including an oxidefilm substrate and organic anti-reflective film (namely no substratedependence is observed) and being excellent in dimension adjustabilityand solution stability.

SUMMARY OF THE INVENTION

Under the situation, the problem to be solved by the present inventionis to provide a resist composition which can form a rectangular patterneven on a special substrate such as SiN, TiN, SiON, BPSG and a strongbasic organic anti-reflective film and is excellent in dimensionadjustability and solution stability.

For the purpose of attaining the object mentioned above, the presentinvention comprises the following embodiments.

(1) An agent for reducing substrate dependence of a resist composition,which comprises a compound shown by the following general formula [1]:

 wherein R₄₁ is a hydrogen atom or a methyl group, R₄₂ is a hydrogenatom, a methyl group, an ethyl group or a phenyl group, R₄₃ is astraight chained, branched or cyclic alkyl group having 1 to 6 carbonatoms, and n is 0 or 1.

(2) A method for reducing substrate dependence of a resist composition,which comprises incorporating as an agent for reducing substratedependence a compound shown by the following general formula [1]:

 wherein R₄₁, R₄₂, R₄₃ and n have the same meaning as above.

(3) A resist composition, which comprises a) a compound shown by thefollowing general formula [1]:

 wherein R₄₁, R₄₂, R₄₃ and n have the same meaning as above, b) apolymer which becomes soluble in an aqueous alkaline developing solutionby a chemical change by an action of an acid, and c) an acid generator(hereinafter abbreviated as the resist composition-1 of the presentinvention).

(4) A resist composition, which comprises a) a compound shown by thefollowing general formula [1]:

 wherein R₄₁, R₄₂, R₄₃ and n have the same meaning as above, b) apolymer soluble in an aqueous alkaline developing solution, c) an acidgenerator, and d) a compound which becomes soluble in an aqueousalkaline developing solution by a chemical change by an action of anacid (hereinafter abbreviated as the resist composition-2 of the presentinvention).

(5) A resist composition, which comprises a) a compound shown by thefollowing general formula [1]:

 wherein R₄₁, R₄₂, R₄₃ and n have the same meaning as above, b) apolymer soluble in an aqueous alkaline developing solution, c) an acidgenerator, and d) a cross-linking compound which can make a polymerhardly soluble in an aqueous alkaline developing solution by a chemicalchange by an action of an acid (hereinafter abbreviated the resistcomposition-3 of the present invention).

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows a cross-section view of positive tone patterns obtained inExamples 1 to 8, which are such good as a rectangular shape withoutfooting.

FIG. 2 shows a cross-section view of patterns on TiN substrate and SiONsubstrate in Comparative Example 1, on silicon substrate using resistcomposition after storage for 3 months in Comparative Example 2, and onTiN substrate in Comparative Examples 3 to 5, which are such bad ones asaccompanied with a round shape on its upper part and footing.

FIG. 3 shows a cross-section view of a bad pattern with peeling off onsilicon substrate and TiN substrate in Comparative Example 2.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

The straight chained, branched or cyclic alkyl group having 1 to 6carbon atoms shown by R₄₃ in the general formula [1] of the presentinvention includes a methyl group, an ethyl group, an n-propyl group, anisopropyl group, a cyclopropyl group, an n-butyl group, an isobutylgroup, a sec-butyl group, a tert-butyl group, an n-pentyl group, anisopentyl group, a cyclopentyl group, an n-hexyl group, a cyclohexylgroup, etc.

Specific examples of the compound shown by the general formula [1] ofthe present invention are methyl glycolate, ethyl glycolate, n-propylglycolate, isopropyl glycolate, n-butyl glycolate, isobutyl glycolate,tert-butyl glycolate, n-pentyl glycolate, isopentyl glycolate, n-hexylglycolate, cyclohexyl glycolate, methyl lactate, ethyl lactate, n-propyllactate, isopropyl lactate, n-butyl lactate, tert-butyl lactate,n-pentyl lactate, isopentyl lactate, methyl 3-hydroxypropionate, ethyl3-hydroxypropionate, n-propyl 3-hydroxypropionate, methyl2-hydroxybutyrate, ethyl 2-hydroxybutyrate, n-propyl 2-hydroxybutyrate,methyl 2-hydroxyisobutyrate, ethyl 2-hydroxyisobutyrate, methyl3-hydroxybutyrate, ethyl 3-hydroxybutyrate, methyl 3-hydroxyvalerate,ethyl 3-hydroxyvalerate, methyl mandelate, ethyl mandelate, n-propylmandelate, isopropyl mandelate, etc.

In the compounds shown by the general formula [1] of the presentinvention, methyl glycolate, ethyl glycolate, ethyl lactate, n-propyllactate, methyl 2-hydroxybutyrate, ethyl 2-hydroxybutyrate, methyl3-hydroxybutyrate, ethyl 3-hydroxybutyrate, methyl mandelate, ethylmandelate, etc. are preferable because they are required to be used onlyin a small amount for reducing substrate dependence and thus control offilm thickness can easily be conducted, among which methyl glycolate,ethyl glycolate, ethyl lactate, methyl 3-hydroxybutyrate, ethyl3-hydroxybutyrate and ethyl mandelate are particularly preferable.

The compound shown by the general formula [1] of the present inventioncan be commercially available and also can easily be obtained by heattreatment of the corresponding hydroxy carboxylic acid and alcohol inthe presence of a strong acid catalyst.

It has been reported that ethyl lactate (ethyl 2-hydroxypropionate),methyl lactate (methyl 2-hydroxypropionate), n-propyl butyrate, ethylglycolate (ethyl hydroxyacetate), methyl 2-hydroxy-2-methylbutyrate,ethyl 3-hydroxypropionate, ethyl 2-hydroxyisobutyrate, methyl4-hydroxybutyrate, ethyl 4-hydroxybutyrate, etc. are alone or incombination (at a 50:50% ratio) used as a solvent for resist composition(e.g. Japanese Patent Publication-Kokai-Nos. 249682/1993, 11836/1994,32817/1994, 28247/1995, 140666/1995, 179508/1996, 211598/1996, etc.),but there has been found no report that those compounds are used as anagent for reducing substrate dependence as in the present invention.Further it has been pointed out that when those hydroxyalkylcarboxylicacid esters are used as the main solvent, there are observed problemsconcerning storage stability as well as poor in control of filmthickness and poor adhesion of substrate (e.g. Japanese PatentPublication-Kokai-No. 11836/1994, etc.).

An amount of the compound shown by the general formula [1] of thepresent invention to be used is preferably 0.5 to 30 wt %, morepreferably 2 to 20 wt %, still more preferably 3 to 15 wt %, relative tothe total amount of the resist composition. Namely, when it is less than0.5 wt %, effect of reduction of substrate dependence is not enough andthus footing pattern is observed, while use in an amount more than 30 wt% is not preferable, because adjustability of film thickness (coatinghomogeneity) is poor and thus dimension is varied on a different levelsubstrate and pattern is peeled off and further due to poor stability ofthe solution, there are caused such problems as variable sensitivity anddimension according to the time lapse.

The compound shown by the general formula [1] of the present inventionmay be used alone or in a suitable combination of two or more thereof.

When used in a suitable combination of two or more of the compounds, atotal amount of the compounds is preferably 0.5 to 30 wt %, morepreferably 2 to 20 wt %, still more preferably 3 to 15 wt %, relative tothe total amount of the resist composition.

A resist composition contains a polymer as one of the essentialingredients. The polymer to be used is grouped into two category, onebeing one itself soluble in an aqueous alkaline developing solution, andthe other being one becoming soluble in an aqueous alkaline developingsolution by a chemical change by an action of an acid. When the formertype is used, a compound which becomes soluble in an aqueous alkalinedeveloping solution by a chemical change by an action of an acid or across-linking compound which can make a polymer hardly soluble in anaqueous alkaline developing solution by a chemical change by an actionof an acid is co-used in order to regulate the solubility, so that apattern can be formed, and in order to generate the acid, an acidgenerator is also used. On the other hand, when the latter type is used,an acid generator is used so that an acid is generated from the acidgenerator and thus generated acid acts upon the polymer in order to makethe polymer soluble in aqueous alkaline developing solution.

The agent for reducing substrate dependence of the present invention canbe used in the above three cases.

The polymer which becomes soluble in an aqueous alkaline developingsolution by a chemical change by an action of an acid mentioned above(hereinafter abbreviated as a polymer having an acid labile group)includes one shown by the general formula [2] or [3];

wherein R and R₁ are independently a hydrogen atom or a methyl group, R₂and R₃ are independently a hydrogen atom, a lower alkyl group or an arylgroup, except for the case where R₂ and R₃ are both hydrogen atoms, andR₂ and R₃ may form together an alkylene ring; R₄ is a lower alkyl groupor an aralkyl group; R₅ is a cyano group, a carboxylic group which maybe esterified or a phenyl group which may be substituted; m and n′ are anatural number; and k is 0 or a natural number, provided that m>k;

wherein R₆ and R₂₁ are independently a hydrogen atom or a methyl group;R₇ is a hydrogen atom, a lower alkyl group, a lower alkoxy group, anacyloxy group, a 5- to 6-membered saturated heterocyclic oxy group or agroup shown by the formula of R₈O—CO—(CH₂)z—O— in which R₈ is an alkylgroup and z is 0 or a natural number; R₂₂ is a cyano group, a phenylgroup which may have a substituent or a carboxyl group which may beesterified; p and r are natural number; f is 0 or a natural number,provided that p>f; with the proviso that when R₇ is a hydrogen atom, alower alkyl group, a lower alkoxy group except for one which is easilychanged into a hydroxy group by an acid, an acyloxy group or a groupR₈O—CO—(CH₂)z—O— (in which R₈ and z have the same meaning as above)except for a case where R₈ is a group labile by an acid, R₂₂ is a phenylgroup having a substituent which is easily changed into a hydroxy groupor a group of —COOR₄₅ (in which R₄₅ is an alkyl group labile by an acid)and that when R₇ is an alkoxy group which is easily changed into ahydroxy group, a 5- to 6-membered saturated oxy group or a group ofR₈O—CO—(CH₂)z—O— (in which R₈ and z have the same meaning as above) inwhich R₈ is labile by an acid, R₂₂ is a cyano group, a phenyl groupwhich may have a substituent or a carboxyl group which may beesterified.

In the above polymer, when a content of the hydroxystyrene units ishigh, the polymer itself is soluble in an aqueous alkaline developingsolution, while it is low, the polymer itself is insoluble and by anaction of an acid, it becomes soluble.

When the content of the hydroxystyrene unit shown by a ratio(n′)/(m+n′+k) in the compound [2] and (r)/(p+r+f) in the compound [3] isless than about 0.8, preferably less than about 0.7, more preferablyless than 0.6, the polymer is insoluble in an aqueous alkalinedeveloping solution and when the content of the hydroxystyrene unitshown by a ratio (n′)/(m+n′+k) in the compound [2] and (r)/(p+r+f) inthe comound [3] is more than about 0.6, preferably more than about 0.7,more preferably more than about 0.8, still more preferably more than0.9, the polymer is soluble in an aqueous developing solution.

The lower alkyl group shown by R₂, R₃ and R₄ in the general formula [2]may be straight chained, branched or cyclic and it is preferably onehaving 1 to 10 carbon atoms, which is specifically exemplified by amethyl group, an ethyl group, an n-propyl group, an isopropyl group, acyclopropyl group, an n-butyl group, an isobutyl group, a tert-butylgroup, a sec-butyl group, an n-pentyl group, an isopentyl group, atert-pentyl group, an 1-methylpentyl group, a cyclopentyl group, ann-hexyl group, an isohexyl group, a cyclohexyl group, a2-cyclohexylethyl gourp, a cyclohexylmethyl group, a heptyl group, anoctyl group, a nonyl group, a decyl group, etc.

The aryl group shown by R₂ and R₃ is specifically exemplified by aphenyl group, a naphtyl group, etc.

The alkylene ring which may be formed together by R₂ and R₃ ispreferably one having 3 to 6 carbon atoms, which is specificallyexemplified by a propylene ring, a butylene ring, a pentylene ring, ahexylene ring, etc.

The aralkyl group shown by R₄ is specifically exemplified by a benzylgroup, a phenethyl group, a phenylpropyl group, a methylbenzyl group, amethylphenetyl group, an ethylbenzyl group, etc.

The carboxyl group which may be esterified shown by R₅ in the generalformula [2] is exemplified by a carboxyl group, one in which a hydrogenatom of a carboxyl group is substituted by an alkyl group having 1 to 6carbon atoms, such as a methoxycarbonyl group, an ethoxycarbonyl group,an n-propoxycarbonyl group, an isopropoxycarbonyl group, ann-butoxycarbonyl group, an isobutoxycarbonyl group, a sec-butoxycarbonylgroup, a tert-butoxycarbonyl group, an n-pentyloxycarbonyl group, atert-pentyloxycarbonyl group, an n-hexyloxycarbonyl group and acyclohexyloxycarbonyl group, one in which a hydrogen atom of a carbonylgroup is substituted by a bridged alicyclic hydrocarbon residue having 7to 9 carbon atoms, such as a norbornyloxycarbonyl group, anisobornyloxycarbonyl group, etc.

The substituent of the phenyl group which may be substituted shown by R₅is exemplified by straight chained, branched or cyclic alkyl group,preferably one having 1 to 10 carbon atoms such as a methyl group, anethyl group, an n-propyl group, an isopropyl group, a cyclopropyl group,an n-butyl group, an isobutyl group, a tert-butyl group, a sec-butylgroup, an n-pentyl group, an isopentyl group, a tert-pentyl group, an1-methylpentyl group, a cyclopentyl group, an n-hexyl group, an isohexylgroup, a cyclohexyl group, a heptyl group, an octyl group, a nonyl groupand a decyl group; a straight chained or branched alkoxy group,preferably one having 1 to 6 carbon atoms, such as a methoxy group, anethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxygroup, an isobutoxy group, a tert-butoxy group, a sec-butoxy group, ann-pentyloxy group, an isopentyloxy group, an n-hexyloxy group and anisohexyloxy group; a straight chained, branched or cyclic acyl grouporiginated from a carboxylic acid having 2 to 7 carbon atoms such as anacetyl group, a propionyl group, an n-butyryl group, an isobutyrylgroup, an n-pentanoyl group, a pivaloyl group, an isovaleryl group and acyclohexane carbonyl group; a 5- to 6-membered saturated heterocyclicoxy group such as tetrahydrofuranyloxy group and tetrahydropyranyloxygroup, and a group shown by the formula of R₂₅O—CO—(CH₂)jO— wherein R₂₅and j have the same meaning as above. The acid labile lower alkyl groupshown by R₂₅ may be branched or cyclic one having 4 to 7 carbon atoms,such as a tert-butyl group, a tert-pentyl group, a 1-methylcyclopentylgroup and a 1-methylcyclohexyl group. The specific examples of the groupshown by the formula R₂₅O—CO—(CH₂)jO— are a tert-butoxycarbonyloxygroup, a tert-pentyloxycarbonyloxy group, a tert-butoxycarbonylmethoxygroup, an 1-methylcyclopentyloxycarbonylmethoxy group, a1-methylcyclohexyloxycarbonylmethoxy group, etc.

The lower alkyl group shown by R₇ in the general formula [3] includespreferably straight chained, branched or cyclic one having 1 to 6 carbonatoms, such as a methyl group, an ethyl group, an n-propyl group, anisopropyl group, a cyclopropyl group, an n-butyl group, an isobutylgroup, a tert-butyl group, a sec-butyl group, an n-pentyl group, anisopentyl group, a tert-pentyl group, a cyclopentyl group, an n-hexylgroup, a 1-methylpentyl group, an isohexyl group and a cyclohexyl group.

The alkoxy group shown by R₇ includes preferably straight chained,branched or cyclic one having 1 to 7 carbon atoms, such as a methoxygroup, an ethoxy group, an n-propoxy group, an isopropoxy group, ann-butoxy group, an isobutoxy group, a tert-butoxy group, a sec-butoxygroup, an n-pentyloxy group, an isopentyloxy group, a tert-pentyloxygroup, an n-hexyloxy group, a 1-methylcyclopentyloxy group, anisohexyloxy group, a heptyloxy group and a 1-methylcycloheyxoxy group.

The acyloxy group shown by R₇ includes preferably straight chained,branched or cyclic one having 2 to 7 carbon atoms derived fromcarboxylic acids, such as an acetyloxy group, a propionyloxy group, ann-butyryloxy group, an isobutyryloxy group, an n-pentanoyloxy group, apivaloyloxy group, an isovarelyloxy group and a cyclohexanecarbonyloxygroup.

The saturated heterocyclic oxy group shown by R₇ is preferably 5- to6-membered one such as a tetrahydrofuranyloxy group and atetrahydropyranyloxy group.

R₈ in R₈O—CO—(CH₂)z—O— includes a straight chained, branched or cyclicalkyl group having 1 to 8 carbon atoms, such as a methyl group, an ethylgroup, an n-propyl group, an isopropyl group, a cyclopropyl group, ann-butyl group, an isobutyl group, a tert-butyl group, a sec-butyl group,an n-pentyl group, an isopentyl group, a 1-methylcyclohexyl group, atert-pentyl group, a 1-methylcyclopentyl group, a cyclopentyl group, ann-hexyl group, an isohexyl group, a cyclohexyl group, a heptyl group andan octyl group, and the specific examples of the group R₈O—CO—(CH₂)z—O—are a methoxycarbonyloxy group, an ethoxycarbonyloxy group, anisopropoxycarbonyloxy group, an isobutoxycarbonyloxy group, atert-butoxycarbonyloxy group, a tert-pentyloxycarbonyloxy group, a1-methylcyclohexyloxycarbonylmethoxy group, a tert-butoxycarbonylmethoxygroup and a 1-methylcyclopentyloxycarbonylmethoxy group.

The substituent of the phenyl group which may have a substituent shownby R₂₂ is exemplified by straight chained, branched or cyclic alkylgroup, preferably one having 1 to 6 carbon atoms such as a methyl group,an ethyl group, an n-propyl group, an isopropyl group, a cyclopropylgroup, an n-butyl group, an isobutyl group, a tert-butyl group, asec-butyl group, an n-pentyl group, an isopentyl group, a tert-pentylgroup, a 1-methylpentyl group, a cyclopentyl group, an n-hexyl group, anisohexyl group and a cyclohexyl group; a straight chained, branched orcyclic alkoxy group, preferably one having 1 to 7 carbon atoms, such asa methoxy group, an ethoxy group, an n-propoxy group, an isopropoxygroup, an n-butoxy group, an isobutoxy group, a tert-butoxy group, asec-butoxy group, an n-pentyloxy group, an isopentyloxy group, atert-pentyloxy group, a 1-methylcyclopentyloxy group, an n-hexyloxygroup, an isohexyloxy group, a heptyloxy group and a1-methylcyclohexyloxy group; a straight chained, branched or cyclicacyloxy group, preferably one having 2 to 7 carbon atoms such as anacetyloxy group, a propionyloxy group, an n-butyryloxy group, anisobutyryloxy group, an n-pentanoyloxy group, a pivaloyloxy group, anisovaleryloxy group and a cyclohexane carbonyloxy group; a 5- to6-membered saturated heterocyclic oxy group such as tetrahydrofuranyloxygroup and tetrahydropyranyloxy group; and a group shown by the formulaof R₂₅O—CO—(CH₂)jO— wherein R₂₅ and j have the same meaning as above,such as a tert-butoxycarbonyloxy group, a tert-pentyloxycarbonyloxygroup, a tert-butoxycarbonylmethoxy group, atert-pentyloxycarbonylmethyloxy group, a1-methylcyclohexyloxycarbonylmethoxy group and a1-methylcyclopentyloxycarbonylmetoxy group.

The carboxylic group which may be esterified shown by R₂₂ is exemplifiedby a carboxyl group, one in which a hydrogen atom of a carboxyl group issubstituted by an alkyl group having 1 to 6 carbon atoms, which isspecifically exemplified by a methoxycarbonyl group, an ethoxycarbonylgroup, an n-propoxycarbonyl group, an isopropoxycarbonyl group, ann-butoxycarbonyl group, an isobutoxycarbonyl group, a sec-butoxycarbonylgroup, a tert-butoxycarbonyl group, an n-pentyloxycarbonyl group, atert-pentyloxycarbonyl group, an n-hexyloxycarbonyl group and acyclohexyloxycarbonyl group, one in which a hydrogen atom of a carbonylgroup is substituted by a bridged alicyclic hydrocarbon residue having 7to 9 carbon atoms, such as a norbornyloxycarbonyl group and anisobornyloxycarbonyl group, etc.

Among the alkoxy group shown by R₇, one which can easily be converted toa hydroxy group by an act of an acid includes a tert-butoxy group, atert-pentyloxy group, a 1-methylcyclopentyloxy group and a1-methylcyclohexyloxy group.

The alkyl group shown by R₈ in the formula R₈O—CO—(CH₂)z—O— which iseasily removed by an act of an acid includes a tert-butyl group, a1-methylcyclohexyl group, a tert-pentyl group, a 1-methylcyclopentylgroup, etc.

The substituent in the substituted phenyl group shown by R₂₂ which iseasily converted to a hydroxy group by an act of an acid includes atert-butoxy group, a tert-pentyloxy group, a 1-methylcyclopentyloxygroup, a 1-methylcyclohexyloxy group, a tetrahydrofuranyloxy group, atetrahydropyranyloxy group, a tert-butoxycarbonyloxy group, atert-pentyloxycarbonyloxy group, a tert-butoxycarbonylmethoxy group, atert-pentyloxycarbonylmethoxy group, a¹-methylcyclohexyloxycarbonylmethoxy group, a1-methylcyclopentyloxycarbonylmethoxy group, etc. The alkyl group shownby R₄₅ in the formula of —COOR₄₅ shown by R₂₂ which is easily removed byan act of an acid includes a tert-butoxycarbonyl group, atert-pentyloxycarbonyl group, etc.

The specific examples of the compound shown by the general formula [2]or [3] are poly(p-tert-butoxystyrene/p-hydroxystyrene),poly(p-tetrahydropyranyloxystyrene/p-hydroxystyrene),poly(p-tert-butoxycarbonyloxystyrene/p-hydroxystyrene),poly(p-1-methoxy-1-methylethoxystyrene/p-hydroxystyrene),poly(p-1-methoxyethoxystyrene/p-hydroxystyrene),poly(p-1-ethoxyethoxystyrene/p-hydroxystyrene),poly(p-1-ethoxypropoxystyrene/p-hydroxystyrene),poly(p-α-ethoxy-4-methylbenzyloxystyrene/p-hydroxystyrene),poly(p-α-ethoxybenzyloxystyrene/p-hydroxystyrene),poly(p-1-ethoxyethoxystyrene/p-tert-butoxystyrene/p-hydroxystyrene),poly(p-1-ethoxyethoxystyrene/p-isopropoxystyrene/p-hydroxystyrene),poly(p-1-ethoxyethoxystyrene/p-tert-butoxycarbonyloxystyrene/p-hydroxystyrene),poly(p-1-ethoxyethoxystyrene/p-tetrahydropyranyloxystyrene/p-hydroxystyrene),poly(p-1-ethoxyethoxystyrene/p-pivarolyloxystyrene/p-hydroxystyrene),poly(p-1-ethoxyethoxystyrene/p-benzoyloxystyrene/p-hydroxystyrene),poly(p-1-ethoxypropoxystyrene/p-tert-butoxystyrene/p-hydroxystyrene),poly(p-1-ethoxypropoxystyrene/p-tert-butoxycarbonyloxystyrene/p-hydroxystyrene),poly(p-1-cyclohexyloxyethoxystyrene/p-tetrahydropyranyloxystyrene/p-hydroxystyrene),poly(p-1-cyclohexyloxyethoxystyrene/p-tert-butoxystyrene/p-hydroxystyrene),poly(p-1-cyclohexyloxyethoxystyrene/p-tert-butoxycarbonyloxystyrene/p-hydroxystyrene),poly[p-1-(2-cyclohexylethoxy)ethoxystyrene/p-acetyloxystyrene/p-hydroxystyrene],poly[p-1-(2-cyclohexylethoxy)ethoxystyrene/p-tert-butoxyxtyrene/p-hydroxystyrene],poly(p-1-cyclohexylmethoxyethoxystyrene/p-tert-butoxystyrene/p-hydroxystyrene),poly(p-1-ethoxyethoxystyrene/styrene/p-hydroxystyrene),poly(p-1-ethoxyethoxystyrene/p-hydroxystyrene/cyclohexyl acrylate),poly(p-1-ethoxyethoxystyrene/p-hydroxystyrene/cyclohexyl methacrylate),poly(p-1-ethoxyethoxystyrene/p-tert-butoxycarbonylmethoxystyrene/p-hydroxystyrene),poly(p-1-ethoxyethoxystyrene/p-hydroxystyrene/isobornyl acrylate),poly(p-1-ethoxyethoxystyrene/p-hydroxystyrene/norbornyl methacrylate),poly(p-1-ethoxypropoxystyrene/p-hydroxystyrene/isobornyl acrylate),poly(p-1-ethoxypropoxystyrene/p-hydroxystyrene/p-tert-butylstyrene),poly(p-1-cyclohexyloxyethoxystyrene/p-hydroxystyrene/isobornylacrylate), poly(p-hydroxystyrene/styrene/tert-butyl acrylate),poly(p-hydroxystyrene/styrene/tert-butyl methacrylate), and partiallycross-linked polymers thereof, etc.

The polymer having an acid labile group which is used in the resistcomposition of the present invention includes those composed of threekinds of monomer units as shown by the above general formula [2] or [3]and also those composed of four kinds of monomer units such aspoly(p-1-ethoxyethoxystyrene/styrene/p-hydroxystyrene/tert-butylacrylate) andpoly(p-1-ethoxyethoxystyrene/styrene/p-hydroxystyrene/tert-butylmethacrylate).

Those polymers may be used alone or in combination of two or morethereof.

The specific examples of the polymer soluble in an aqueous alkalinedeveloping solution used in the resist composition-2 or -3 of thepresent invention are poly(p-hydroxystyrene),poly(styrene/p-hydroxystyrene) [among them, one having a ratio ofstyrene units to p-hydroxystyrene units is limited to 4 or less:6 ormore (such a ratio is hereinafter represented by 4↓:6↑) is preferable],poly(p-tert-butoxystyrene/p-hydroxystyrene) [among them, one having aratio of p-tert-butoxystyrene units to p-hydroxystyrene units of 2↓:8↑is preferable], poly(p-isopropoxystyrene/p-hydroxystyrene) [among them,one having p-isopropoxystyrene units to p-hydroxystyrene units of 2↓:8↑is preferable], poly(p-tetrahydropyranyloxystyrene/p-hydroxystyrene)[among them, one having p-tetrahydropyranyloxystyrene units top-hydroxystyrene units of 2↓:8↑ is preferable], poly(tert-butoxycarbonyloxystyrene/p-hydroxystyrene) [among them, one havingtert-butoxycarbonyloxystyrene units to p-hydroxystyrene units of 2↓:8↑is preferable], poly(p-1-ethoxyethoxystyrene/p-hydroxystyrene) [amongthem, one having p-1-ethoxyethoxystyrene units to p-hydrdoxystyreneunits of 2↓:8↑ is preferable],poly(p-1-ethoxyethoxystyrene/p-tert-butoxystyrene/p-hydroxystyrene)[among them, one having a ratio of the sum of p-1-ethoxyethoxystyreneunits and p-tert-butoxystyrene units to p-hydroxystyrene units of 2↓:8↑is preferable], poly(p-1-ethoxyethoxystyrene/styrene/p-hydroxystyrene)[among them, one having a ratio of the sum of p-1-ethoxyethoxystyreneunits and styrene units to p-hydroxystyrene units of 2↓:8↑ ispreferable], poly(p-hydroxystyrene/styrene/tert-butyl acrylate) [amongthem, one having a ratio of p-hydroxystyrene units to the sum of styreneunits and tert-butyl acrylate units of 7↑:3↓ is preferable],poly(p-hydroxystyrene/styrene/tert-butyl methacrylate) [among them, onehaving a ratio of p-hydroxystyrene units to the sum of styrene units andtert-butyl methacrylate units of 7↑:3↓ is preferable], etc.

The polymer having an acid labile group and the polymer soluble in anaqueous alkaline developing solution of the present invention can beobtained by a radical polymerization with the use of an organicperoxide, an azo type compound, etc. as a polymerization initiator and aliving polymerization with the use of n-butyl lithium, sec-butyllithium, etc., followed by sujecting the resulting polymer to a chemicalreaction upon necessity. More specifically, they can easily be obtainedby the method disclosed in Japanese Patent Publication-Kokoku-No.36602/1988, Japanese Patent Publication-Kokai-No. 211258/1992,249682/1993, 123032/1996, 53621/1998, 207066/1998, etc.

A molecular weight and a dispersity (a ratio of a weight averagemolecular weight to a number averate molecular weight, Mw/Mn) of thepolymer having an acid labile group and the polymer soluble in anaqueous alkaline developing solution of the present invention are 1,000to 50,000, preferably 2,000 to 30,000 and 1.0 to 3.0, preferably 1.0 to2.0, respectively by GPC measurement method using polystyrene as astandard.

The compound which becomes soluble in an aqueous alkaline developingsolution by a chemical change by an action of an acid (hereinafter,abbreviated as a dissolving inhibitor agent having an acid labile group)used in the resist composition-2 of the present invention includes analkaline insoluble compound in which a part or all of phenolic hydroxygroups in an alkaline soluble compound having phenolic hydroxy groupsare protected by a tert-butoxycarbonyl group, a tert-butyl group, an1-methoxyethyl group, an 1-ethoxyethyl group, a tetrahydropyranyl group,an 1-methylcyclohexyloxycarbonylmethyl group, etc.

More specifically, the compound includes one shown by the followinggeneral formula [16] or [17]

wherein R₅₁ is an alkyl group, an alkoxycarbonyl group, an alkoxyalkylgroup, a tetrahydrofuranyl group or a tetrahydropyranyl group, s is 1 to3, Y is a divalent or trivalent aliphatic hydrocarbon residue which mayhave a substituent, (R₅₁—O)s means that s numbers (in which s is 2 or 3)of the group (R₅₁—O) are substituted at the benzene ring, and a carbonatom in the hydrocarbon residue of Y and a carbon atom in the groupshown R₅₁ may form together an aliphatic ring such astetrahydropyranyloxy substituted by a lower alkyl group, including1,1,3-trimethyl tetrahydropyranyloxy group. The alkyl group and thealkyl group in alkoxyalkyl group include one having 1 to 6 carbon atoms,such as a methyl group, an ethyl group, an n-propyl group, anisopropylgroup, an n-butyl group, an iso-butyl group, a tert-butylgroup, an n-pentyl group, an isopentyl group, an n-hexyl group, aniso-hexyl group. The alkoxy group in the alkoxycarbonyl group and thealkoxyalkyl group include one having 1 to 6 carbon atoms, such as amethoxy group, an ethoxy group, an n-propoxy group, an iso-propoxygroup, an n-butoxy group, an iso-butoxy group, a tert-butoxy group, ann-pentoxy group, an iso-pentoxy group, an n-hexyloxy group and aniso-hexyloxy group. The aliphatic hydrocarbon residue shown by Yincludes a straight chained, branched or cyclic alkylene group having 1to 6 carbon atoms such as a methylene group, an ethylene group, amethylmethylene group, a propylene group, an 1-methylethylene group, an1,1-dimethylmethylene group, a butylene group, a hexylene group; astraight chained, branched or cyclic alkane triyl group having 2 to 6carbon atoms an ethane triyl group, a propane triyl group, an1-methylethane triyl group, an 1,1-dimethylmethane triyl group, a butanetriyl group, a hexane triyl group. The substituent in Y includes analkoxy group, an alkoxycarbonyl group and an aryl group which may have asubstituent. The alkoxy group and the alkoxy group in the alkoxycarbonylgroup includes one having 1 to 6 carbon atoms, such as a methoxy group,an ethoxy group, an n-propoxy group, an iso-propoxy group, an n-butoxygroup, an iso-butoxy group, a tert-butoxy group, an n-pentoxy group. Thearyl group includes a phenyl group, a naphtyl group etc. The substituentof the aryl group includes an aralkyl group, which may have asubstituent such as a straight chaned, brancherd or cyclic alkyl grouphaving 1 to 6 carbon atoms and an straight chained, branced or cyclicalkoxy group having 1 to 6 carbon atoms, such as a benzyl group, aphenethyl group, a phenylpropyl group, a methylbenzyl group, amethylphenetyl group, an ethylbenzyl group, and a dimethyl phenyl methylgroup, etc.

The specific examples of the compound includes2,2-bis(4-tert-butoxycarbonyloxyphenyl)propane,2,2-bis(4-tert-butoxyphenyl)propane,2,2-bis(4-tetrahydropyranyloxyphenyl)propane,2,2-bis[4-(1-ethoxyethoxyphenyl)]propane, 2,2-bis(4-tertbutoxycarbonyloxyphenyl)butane, 2,2-bis(4-tert-butoxyphenyl)butane,2,2-bis(4-tetrahydrofuranyloxyphenyl)butane,2,2-bis[4-(1-ethoxyethoxyphenyl)]-4-methylpentane,3,3-bis(4-tert-butoxycarbonylmethoxyphenyl)butane,1,1,1-tris(4-tert-butoxycarbonyloxyphenyl)ethane,1,1,1-tris(4-tetrahydropyranyloxyphenyl)ethane,α,α,α′-tris(4-tert-butoxycarbonyloxyphenyl)-1-ethyl-4-isopropylbenzene,α,α,α′-tris(4-tetrahydropyranyloxyphenyl)-1-ethyl-4-isopropylbenzene,3,4-dihydro-4-[2,4-di-(1-ethoxyethoxy)phenyl]-7-(1-ethoxyethoxy)-2,2,4-trimethyl-2H-benzo-1-pyran,3,4-dihydro-4-(2,4-di-tetrahydropyranyloxyphenyl)-7-tetrahydropyranyloxy-2,2,4-trimethyl-2H-benzo-1-pyran,tert-butyl 2,2-bis(4-tert-butoxycarbonyloxyphenyl)pentanonate, etc.

Those compounds may be used alone or in combination of two or morethereof.

As the polymer which becomes soluble in an aqueous alkaline developingsolution by a chemical change by an action of an acid used in the resistcomposition-2 of the present invention, the same polymer as the polymerhaving an acid labile group used in the resist composition-1 mentionedabove can be used.

The cross-linking compound which can make a polymer hardly soluble in anaqueous alkaline developing solution by a chemical change by an actionof an acid, which is used the resist composition-3 of the presentinvention includes a compound shown by the following general formula[4];

wherein R₃₆ is an alkyl group, R₃₇ is a hydrogen atom or a group shownby the general formula [5]:

wherein R₃₆ has the same meaning as above, or one shown by the generalformula [6];

wherein R₃₈ is a hydrogen atom or an alkyl group, and R₃₉ is a hydrogenatom or a group shown by the general formula [7]:

wherein R₃₈ has the same meaning as above.

The alkyl group shown by R₃₆ in the general formula [4] and [5] and oneshown by R₃₈ in the general formula [6] and [7] may be straight chained,branched or cyclic and preferably one having 1 to 6 carbon atoms, whichis specifically exemplified by a methyl group, an ethyl group, ann-propyl group, an isopropyl group, a cyclopropyl group, an n-butylgroup, an isobutyl group, a tert-butyl group, a sec-butyl group, ann-pentyl group, an isopentyl group, a tert-pentyl group, a1-methylpentyl group, a cyclopentyl group, an n-hexyl group, an isohexylgroup, a cyclohexyl group, etc.

The cross-linking agent used in the resist composition-3 of the presentinvention includes specifically2,4,6-tris(methoxymethyl)amino-1,3,5-s-triazine,2,4,6-tris(ethoxymethyl)amino-1,3,5-s-triazine, tetramethoxymethylglycolurea, tetramethoxymethyl urea, 1,3,5-tris(methoxymethoxy)benzene,1,3,5-tris(isopropoxymethoxy)benzene,α,α,α′-tris(isopropoxymethoxyphenyl)-1-ethyl-4-isopropylbenzene,α,α,α′-tris(methoxymethoxyphenyl)-1-ethyl-4-isopropylbenzene, CY-179(Trade name of product manufactured and sold by Ciba-Geigy A.-G.), etc.Those compounds may be used alone or in combination of two or morethereof.

The compound generating an acid by actinic radiation, which is used inthe resist compositions-1, 2 and 3 of the present invention(hereinafter, abbreviated as an acid generator) may be any one which cangenerate an acid by actinic radiation and gives no bad influence uponresist pattern formation, and includes preferably one which shows goodtransmittance around 248.4 nm and thus can keep high transparency of aresist material and one which can keep high transparency of a resistmaterial in which transmittance around 248.4 nm is increased byexposure. Such particularly preferable acid generator as above includescompound shown by the general formula [8], [9], [11], [12], [13 ] and[15];

wherein R₉ and R₁₀ are independantly an alkyl group or a haloalkyl groupand A′ is a sulfonyl group or a carbonyl group;

wherein R₁₁ is a hydrogen atom, an alkyl group, an alkoxy group or ahaloalkyl group, and R₁₂ is an alkyl group, a haloalkyl group or a groupshown by the following general formula [10]:

wherein R₁₃ is a hydrogen atom, a halogen atom, an alkyl group, analkoxy group or a haloalkyl group, and q is 0 or an integer of 1 to 3;

wherein R₁₄ is a hydrogen atom, a halogen atom, an alkyl group or atrifluoromethyl group and R₁₅ is an alkyl group, an aralkyl group, analkoxy group, a phenyl group or a tolyl group;

wherein R₁₆ is an alkyl group, a phenyl group, a substituted phenylgroup or an aralkyl group, R₁₇ and R₁₈ are independently a hydrogenatom, an alkyl group, a phenyl group, a substituted phenyl group or anaralkyl group, and R₁₉ is a fluoroalkyl group, a trifluoromethylphenylgroup, a methyl group or tolyl group;

wherein R₂₉ is an alkyl group, a fluoroalkyl group, a phenyl group, asubstituted phenyl group or an aralkyl group, Q′ is a sulfonyl group ora carbonyl group, R₃₀ and R₃₁ are independently a hydrogen atom, amethyl group, a methoxy group, a nitro group, a cyano group, a hydroxygroup or a group shown by the following general formula [14]:

wherein R₃₃ is an alkyl group, a fluoroalkyl group, a phenyl group, asubstituted phenyl group or an aralkyl group, Q′ is a sulfonyl group ora carbonyl group, and R₃₂ is a hydrogen atom, a methyl group or an ethylgroup;

wherein R₃₄ is an alkyl group, a fluoroalkyl group, a phenyl group, asubstituted phenyl group or an aralkyl group, R₃₅ is a hydrogen atom, amethyl group, a fluoroalkyl group, a methoxy group, a nitro group, acyano group, a hydroxy group or a group shown by the above generalformula [14].

The alkyl group or the alkyl group in the haloalkyl group shown by R₉and R₁₀ in the general formula [8] may be straight chained, branched orcyclic, preferably one having 1 to 10 carbon atoms, which isspecifically exemplified by a methyl group, an ethyl group, an n-propylgroup, an isopropyl group, a cyclopropyl group, an n-butyl group, anisobutyl group, a tert-butyl group, a sec-butyl group, an n-pentylgroup, an isopentyl group, a tert-pentyl group, an 1-methylpentyl group,a cyclopentyl group, an n-hexyl group, an isohexyl group, a cyclohexylgroup, a heptyl group, an octyl group, a nonyl group, a decyl group,etc.

The halogen atm in the haloalkyl group includes chlorine, bromine,fluorine and iodine, etc.

The alkyl group or the alkyl group in the haloalkyl group shown by R₁₁in the general formula [9] may be straight chained or branched,preferably one having 1 to 5 carbon atoms, which is specificallyexemplified by a methyl group, an ethyl group, an n-propyl group, anisopropyl group, an n-butyl group, an isobutyl group, a tert-butylgroup, a sec-butyl group, an n-pentyl group, an isopentyl group, atert-pentyl group, a 1-methylpentyl group, etc; the halogen atom orhalogen atm in the haloalkyl group shown by R₁₁ includes chlorine,bromine, fluorine and iodine. The alkoxy group shown by R₁₁ may bestraight chained or branched, preferably one having 1 to 5 carbon atoms,which is specifically exemplified by a methoxy group, an ethoxy group,an n-propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxygroup, a tert-butoxy group, a sec-butoxy group, an n-pentyloxy group, anisopentyloxy group, etc. The alkyl group or the alkyl group in thehaloalkyl group shown by R₁₂ may be straight chained, branched or cyclicone, preferably one having 1 to 10 carbon atoms, which is specificallyexemplified by a methyl group, an ethyl group, an n-propyl group, anisopropyl group, a cyclopropyl group, an n-butyl group, an isobutylgroup, a tert-butyl group, a sec-butyl group, an n-pentyl group,anisopentyl group, a tert-pentyl group, a 1-methylpentyl group, acyclopentyl group, an n-hexyl group, an isohexyl group, a cyclohexylgroup, a heptyl group, an octyl group, a nonyl group, a decyl group,etc; the halogen atm in the haloalkyl group includes chlorine, bromine,fluorine and iodine.

The alkyl group or the alkyl group in the haloalkyl group shown by R₁₃in the general formula [10] may be straight chained or branched one andpreferably one having 1 to 6 carbon atoms, which is specificallyexemplified by a methyl group, an ethyl group, an n-propyl group, anisopropyl group, an n-butyl group, an isobutyl group, a tert-butylgroup, a sec-butyl group, an n-pentyl group, an isopentyl group, atert-pentyl group, a 1-methylpentyl group, an n-hexyl group, an isohexylgroup, etc. The alkoxy group shown by R₁₃ having 1 to 6 carbon atoms maybe straight chained or branched, preferably one having 1 to 5 carbonatoms, which is specifically exemplified by a methoxy group, an ethoxygroup, an n-propoxy group, an isopropoxy group, an n-butoxy group, anisobutoxy group, a tert-butoxy group, a sec-butoxy group, an n-pentyloxygroup, an isopentyloxy group, an hexyloxy group, an isohexyloxy group,etc., and the halogen atom or halogen atom in the haloalkyl group shownby R₁₃ includes chlorine, bromine, fluorine and iodine.

The alkyl group or the alkyl group in the haloalkyl group shown by R₁₄in the general formula [11] may be straight chained or branched andpreferably one having 1 to 5 carbon atoms, which is specificallyexemplified by a methyl group, an ethyl group, an n-propyl group, anisopropyl group, an n-butyl group, an isobutyl group, a tert-butylgroup, a sec-butyl group, an n-pentyl group, an isopentyl group, atert-pentyl group, a 1-methylpentyl group, etc. The halogen atom shownby R₁₄ includes chlorine, bromine, fluorine and iodine. The alkyl groupshown by R₁₅ may be straight chained, branched or cyclic and preferablyone having 1 to 10 carbon atoms, which is specifically exemplified by amethyl group, an ethyl group, an n-propyl group, an isopropyl group, acyclopropyl group, an n-butyl group, an isobutyl group, a tert-butylgroup, a sec-butyl group, an n-pentyl group, an isopentyl group, atert-pentyl group, a 1-methylpentyl group, a cyclopentyl group, ann-hexyl group, an isohexyl group, a cyclohexyl group, a heptyl group, anoctyl group, a nonyl group, a decyl group, etc.

The aralkyl group shown by R₁₅ includes a benzyl group, a phenethylgroup, a phenylpropyl group, a methylbenzyl group, a methylphenethylgroup, an ethylbenzyl group, etc. The alkoxy group shown by R₁₅ may bestraight chained or branched and is exemplified by one having 1 to 6carbon atoms such as a methoxy group, an ethoxy group, an n-propoxygroup, an isopropoxy group, an n-butoxy group, an isobutoxy group, atert-butoxy group, a sec-butoxy group, an n-pentyloxy group, anisopentyloxy group, an n-hexyloxy group and an isohexyloxy group.

The alkyl group shown by R₁₆, R₁₇ and R₁₈ in the general formula [12]may be straight chained, branched or cyclic and preferably one having 1to 8 carbon atoms, which is specifically exemplified by a methyl group,an ethyl group, an n-propyl group, an isopropyl group, a cyclopropylgroup, an n-butyl group, an isobutyl group, a tert-butyl group, asec-butyl group, an n-pentyl group, an isopentyl group, a tert-pentylgroup, a 1-methylpentyl group, a cyclopentyl group, an n-hexyl group, anisohexyl group, a cyclohexyl group, a heptyl group, an octyl group,etc., and the substituted phenyl group includes a tolyl group, anethylphenyl group, a tert-butylphenyl group, a chlorophenyl group, etc.The aralkyl group includes a benzyl group, a phenethyl group, aphenylpropyl group, a methylbenzyl group, a methylphenethyl group, anethylbenzyl group, etc. The alkyl of the fluoroalkyl group shown by R₁₉may be straight chained or branched, preferably one having 1 to 8 carbonatoms, which is specifically exemplified by a methyl group, an ethylgroup, an n-propyl group, an isopropyl group, an n-butyl group, anisobutyl group, a tert-butyl group, a sec-butyl group, an n-pentylgroup, an isopentyl group, a tert-pentyl group, a 1-methylpentyl group,an n-hexyl group, an isohexyl group, a heptyl group, an octyl group,etc., and the total number of the fluorine atoms substituted ispreferably 1 to 17.

The alkyl group shown by R₂₉ in the general formula [13] may be straightchained, branched or cyclic and preferably one having 1 to 6 carbonatoms, which is specifically exemplified by a methyl group, an ethylgroup, an n-propyl group, an isopropyl group, an n-butyl group, anisobutyl group, a tert-butyl group, a sec-butyl group, an n-pentylgroup,an isopentyl group, a cyclopentyl group, an n-hexyl group, acyclohexyl group, etc., the substituted phenyl group includes a tolylgroup, an ethylphenyl group, a tert-butylphenyl group, a chlorophenylgroup, etc., and the aralkyl group includes a benzyl group, a phenethylgroup, a phenylpropyl group, a methylbenzyl group, a methylphenethylgroup, an ethylbenzyl group, etc. The alkyl group in the fluoroalkylgroup may be straight chained or branched and preferably one having 1 to8 carbon atoms, which is specifically exemplified by a methyl group, anethyl group, an n-propyl group, an isopropyl group, an n-butyl group, anisobutyl group, a tert-butyl group, a sec-butyl group, an n-pentylgroup, an isopentyl group, an n-hexyl group, a heptyl group, an octylgroup, etc. The total number of the fluorine atoms substituted ispreferably 1 to 17.

The alkyl group shown by R₃₃ in the general formula [14] may be straightchained, branched or cyclic and preferably one having 1 to 6 carbonatoms, which is specifically exemplified by a methyl group, an ethylgroup, an n-propyl group, an isopropyl group, an n-butyl group, anisobutyl group, a tert-butyl group, a sec-butyl group, an n-pentylgroup, an isopentyl group, a cyclopentyl group, an n-hexyl group, acyclohexyl group, etc., the substituted phenyl group includes a tolylgroup, an ethylphenyl group, a tert-butylphenyl group, a chlorophenylgroup, etc., and the aralkyl group includes a benzyl group, a phenethylgroup, a phenylpropyl group, a methylbenzyl group, a methylphenethylgroup, an ethylbenzyl group, etc. The alkyl group in the fluoroalkylgroup may be straight chained or branched and preferably one having 1 to8 carbon atoms, which is specifically exemplified by a methyl group, anethyl group, an n-propyl group, an isopropyl group, an n-butyl group, anisobutyl group, a tert-butyl group, a sec-butyl group, an n-pentylgroup, an isopentyl group, an n-hexyl-group, a heptyl group, an octylgroup, etc. The total number of the fluorine atoms substituted ispreferably 1 to 17.

The alkyl group shown by R₃₄ in the general formula [15] may be straightchained, branched or cyclic and preferably one having 1 to 6 carbonatoms, which is specifically exemplified by a methyl group, an ethylgroup, an n-propyl group, an isopropyl group, an n-butyl group, anisobutyl group, a tert-butyl group, a sec-butyl group, an n-pentylgroup, an isopentyl group, a cyclopentyl group, an n-hexyl group, acyclohexyl group, etc., the substituted phenyl group includes a tolylgroup, an ethylphenyl group, a tert-butylphenyl group, a chlorophenylgroup, etc., and the aralkyl group includes a benzyl group, a phenethylgroup, a phenylpropyl group, a methylbenzyl group, a methylphenethylgroup, an ethylbenzyl group, etc. The alkyl group in the fluoroalkylgroup shown by R₃₄ and R₃₅ may be straight chained or branched andpreferably one having 1 to 8 carbon atoms, which is specificallyexemplified by a methyl group, an ethyl group, an n-propyl group, anisopropyl group, an n-butyl group, an isobutyl group, a tert-butylgroup, a sec-butyl group, an n-pentyl group, an isopentyl group, ann-hexyl group, a heptyl group, an octyl group, etc. The total number ofthe fluorine atoms substituted is preferably 1 to 17.

As specific preferable examples of the acid generators used in thepresent invention, one shown by the general formula [8] includes1-cyclohexylsulfonyl-1-(1,1-dimethylethylsulfonyl)diazomethane,bis(1,1-dimethylethylsulfonyl)diazomethane,bis(1-methylethylsulfonyl)diazomethane,bis(cyclohexylsulfonyl)diazomethane,1-cyclohexylsulfonyl-1-cyclohexylcarbonyl diazomethane,1-diazo-1-cyclohexylsulfonyl-3,3-dimethylbutane-2-on,1-diazo-1-methylsulfonyl-4-phenylbutane-2-on,1-diazo-1-(1,1-dimethylethylsulfonyl)-3,3-dimethyl-2-butanone,1-acetyl-1-(1-methylethylsulfonyl)diazomethane, etc.

The acid generator shown by the general formula [9] includesbis(p-toluenesulfonyl)diazomethane,bis(2,4-dimethylbenzenesulfonyl)diazomethane,methylsulfonyl-p-toluenesulfonyl diazomethane,bis(p-tert-butylphenylsulfonyl)diazomethane,bis(p-chlorobenzenesulfonyl)diazomethane,cyclohexylsulfonyl-p-toluenesulfonyl diazomethane, etc.

The acid generator shown by the general formula [11] includes1-p-toluenesulfonyl-1-cyclohexycarbonyl diazomethane,1-diazo-1-(p-toluenesulfonyl)-3,3-dimethylbutane-2-on,1-diazo-1-benzenesulfonyl-3,3-dimethylbutan-2-on,1-diazo-1-(p-toluenesulfonyl)-3-methylbutane-2-on, etc.

The acid generator shown by the general formula [12] includestriphenylsulfonium/trifluoromethanesulfonate,triphenylsulfonium/perfluorobutanesulfonate,triphenylsulfonium/perfluorooctanesulfonate,triphenylsulfonium/p-toluenesulfonate,diphenyl-p-tolylsulfonium/perfluorooctanesulfonate,diphenyl-p-tolylsulfonium/trifluoromethanesulfonate,diphenyl-p-tolylsulfonium/p-toluenesulfonate,diphenyl-p-tolylsulfonium/perfluorobutanesulfonate,diphenyl-p-tert-butylphenylsulfonium/perfluorooctanesulfonate,diphenyl-p-tert-butylphenylsulfonium/p-toluenesulfonate,tris(p-tolyl)sulfonium/perfluorooctanesulfonate,tris(p-chlorophenyl)sulfonium/trifluoromethanesulfonate,tris(p-tolyl)sulfonium/trifluoromethanesulfonate,trimethylsulfonium/trifluoromethanesulfonate,dimethylphenylsulfonium/trifluoromethanesulfonate,dimethyl-p-tolylsulfonium/trifluoropethanesulfonate,dimethyl-p-tolylsulfonium/perfluorooctanesulfonate, etc.

The acid generator shown by the general formula [13] includes2,6-di-trifluoromethanesulfonyloxyacetophenone,2,6-di-trifluoromethanesulfonyloxypropiophenone,2,3,4-tris-trifluoromethanesulfonyloxyacetophenone,2,6-di-methanesuflonyloxyacetophenone,2,6-di-methanesulfonyloxypropiophenone,2,3,4-tris-methanesulfonyloxyacetophenone,2-trifluoromethanesulfonyloxyacetophenone,2-methanesulfonyloxyacetophenone, 2-n-butanesuflonyloxyacetophenone,2,6-di-n-butanesulfonyloxyacetophenone,2,3,4-tris-n-butanesulfonyloxyacetophenone,2,6-di-perfuloropropanecarboxyacetophenone,2,3,4-tris-perfluoropropanecarboxyacetophenone,2,6-di-p-toluenesuflonylacetophenone,2,6-di-p-toluenesulfonylpropiophenone,2,6-di-trifluoroacetyloxyacetophenone,2-trifluoroacetyloxy-6-methoxyacetophenone,6-hydroxy-2-perfluorobutanesulfonyloxyacetophenone,2-trifluoroacetyloxy-6-nitroacetophenone,2,3,4-tris-trifluoroacetyloxyacetophenone,2,6-di-perfluoropropanoyloxyacetophenone, etc.

The acid generator shown by the general formula [15] includes1,2,3-tris-methanesulfonyloxybenzene,1,2,3-tris-p-toluenesulfonyloxybenzene,1,2,3-tris-trifluoromethanesulfonyloxybenzene,1,2,3-tris-perfluorobutanesulfonyloxybenzene,1,2,3-tris-cyclohexylsulfonyloxybenzene,1,2-di-methanesulfonyloxy-3-nitrobenzene,2,3-di-methanesulfonyloxyphenol, 1,2,4-tris-p-toluenesulfonyloxybenzene,1,2,4-tris-methanesulfonyoxybenzene,1,2,4-tris-trifluoromethanesulfonyloxybenzene,1,2,4-tris-cyclohexylsulfonyloxybenzene,1,2-di-n-butanesulfonyloxy-3-nitrobenzene,1,2,3-tris-perfluorooctanesulfonyloxybenzene,1,2-di-perfluorobutanesulfonyloxyphenol, etc.

The acid generator of the present invention can easily be obtained bymethods disclosed in Japanese Patent Publication-Kokai-Nos. 210960/1992,211258/1992, 249682/1993, etc.

Those acid generator may be used alone or in combinations of two or morethereof.

The solvent used in the present invention may be any one which candissolve the above mentioned compound, the polymer, the cross-linkingagent, the acid generator and a basic compound, a surfactant, an UVabsorber, dissolving accelerator, etc. which may be used upon necessity,and use is generally made of those showing good film-formation ability,such as methyl cellosolve acetate, ethyl cellosolve acetate,propyleneglycol monomethylether acetate, propyleneglycol monoethyletheracetate, 2-heptanone, methyl 3-methoxy propionate, cyclohexanone, butylacetate, diethyleneglycol dimethylether, etc.

An amount of the polymer having an acid labile group in the resistcomposition-1 of the present invention and the polymer soluble in anaqueous alkaline developing solution in the resist compositions-2 or -3of the present invention which are occupied in the resist compositiondepend upon the thickness of the final resist film to be attained andare each generally 5 to 25 wt %, preferably 10 to 20 wt %.

An amount of the dissolving inhibitor having an acid labile group and/orthe polymer having an acid labile group in the resist composition-2 ofthe present invention is 1 to 50 wt %, preferably 1 to 25 wt %, relativeto the polymer soluble in an aqueous alkaline developing solution.

An amount of the cross-linking agent in the resist composition-3 of thepresent invention is 3 to 20 wt %, preferably 5 to 15 wt %, relative tothe polymer soluble in an aqueous alkaline developing solution.

An amount of the acid generator of the present invention to be used is0.1 to 20 wt %, preferably 0.5 to 15 wt %, relative to the polymerhaving an acid labile group in the resist composition-1 of the presentinvention and relative to the polymer soluble in an aqueous alkalinedeveloping solution in the resist compositions-2 and -3 of the presentinvention, respectively.

An amount of the solvent of the present invention to be used is 50 to 95wt %, preferably 60 to 90 wt %, relative to the total amount of theresist composition.

In the resist compositions of the present invention, use can be made ofa basic compound, a surfactant, an UV absorber, a dissolvingaccelerator, etc., upon necessity, in addition to the above mentionedmain ingredients.

The basic compound to be used in the resist compositions of the presentinvention upon necessity includes pyridine, picoline, triethylamine,tri-n-butylamine, tri-n-octylamine, dioctylmethylamine,dicyclohexylmethylamine, dimethyldodecylamine, dimethylhxadecylamine,N-methylpyrrolidine, N-methylpiperidine, triethanolamine,tris[2-(2-methoxyethoxy)ethyl]amine, tetramethylammonium hydroxide,tetrabutylammonium hydroxide, polyvinylpyridine, etc. They may be usedalone or in combination of two or more thereof.

An amount of the basic compound of the present invention to be used is0.05 to 1.0 wt %, preferably 0.1 to 0.5 wt %, relative to the totalamount of the resist composition.

The surfactant to be used upon necessity in the resist compositions ofthe present invention includes a nonionic one (e.g. polyethylene glycoldistearate, polyethylene glycol dilaurate, poly(ethylene glycol),poly(propylene glycol), polyoxyethylene cetyl ether), an anionicsurfactant, a cationic surfactant, a fluorine-containing anionicsurfactant, a fluorine-containing cationic surfactant, afluorine-containing nonionic surfactant [e.g. Fluorad (a trade name ofSumitomo 3M, Ltd.), Surflon (a trade name of Asahi Glass Co., Ltd.),Unidyne (a trade name of Daikin Industries, Ltd.), Megafac (a trade nameof Dainippon Ink & Chemicals, Inc.) and Eftop (a trade name of TohkemProducts Corp.)], etc. They may be used alone or in combination of twoor more thereof.

An amount of the surfactant to be used may be selected from a rangewhich has been generally used in this kind of technical field.

The UV absorber used upon necessity in the resist composition of thepresent invention includes 9-diazofluorenone, 9-(2-methoxyethoxymethyl)anthracene, 9-(2-ethoxyethoxymethyl)anthracene, 9-fluorenone,2-hydroxycarbazole, o-naththoquinone diazide derivative,4-diazo-1,7-diphenylpentane-3,5-dione, etc. They may be used alone or incombination of two or more thereof.

An amount of the UV-absorber to be used in the present invention may beselected from a range which has been generally used in this kind oftechnical field.

The dissolving accelerator to be used upon necessity in the resistcomposition of the present invention includes N,N-dimethylformamide,N,N-dimethylacetamide, γ-butyrolactone, etc. They may be used alone orin combination of two or more thereof.

An amount of the dissolving accelerator to be used in the presentinvention may be selected from a range which has been used generally inthis kind of technical field.

As the aqueous alkaline developing solution of the present invention,use is made of 0.5 to 5 wt % diluted aqueous solution oftetramethylammonium hydroxide, choline, potassium hydroxide, sodiumhydroxide, etc. There may be incorporated a surfactant and alcoholiccompound in the aqueous alkaline developing solution in order toincrease an affinity to the resist composition.

The pattern formation using the chemically-amplified resist compositionof the present invention can be conducted as follows.

The resist composition of the present invention is spin-coated on asemiconductor substrate plate such as SiO₂ (oxide film), polysilicon,SiN, SiON, TiN, basic organic anti-reflective film, etc., and baked on ahot plate at 50 to 120° C. for 0.5 to 2 minutes to obtain a resist filmof 0.3 to 2 μm thick. Then radiation (e.g. 248.4 nm KrF excimer laser,300 nm or less deep UV, electron beam, soft X-ray, etc.) is irradiatedselectively on the surface through a mask, and then if necessary baked(post baked) on a hot plate at 50 to 150° C. for 0.5 to 2 minutes,followed by developing with the use of an aqueous alkaline developingsolution by a puddle method, a dip method, a spray method, etc., wherebythe desired positive tone or negative tone pattern is formed due to adifference in solubility in the developing solution between the exposeportion and the non-exposed portion.

The reason why the substrate dependency, the problem in achemically-amplified resist, can be reduced by addition of the compoundshown by the general formula [1] of the present invention, isconsidered, though not clearly explained, as follows in a case where thepolymer having an acid labile group and/or the dissolution inhibitorhaving an acid labile group are used. Namely, for instance, in a casewhere the resist composition-1 of the present invention (containing thepolymer having an acid labile group) containing the compound shown bythe general formula [1] is coated on a substrate and pre-baked to form aresist film, there occurs such a reaction as a part of the acid labilegroup of the polymer having an acid labile group being removed by analcoholic hydroxy group of the compound shown by the general formula [1](see the following equation 1).

This reaction occurs regardless of whether the acid generated by theacid generator by an actinic radiation is deactivated by a basicsubstance or water generated from the specific substrate such as SiN,TiN, SiN, BPSG, a basic organic anti-reflective film, etc., and isaccelerated by heating, and therefore, there is found suchcharacteristics that this reaction occurs much remarkably around thesubstrate. Thus, it is considered that when a resist film is formed andthen as pattern is formed with the use of the resist compositioncontaining the compound shown by the formula [1] of the presentinvention after the usual manner, the resist around the substratebecomes eaily soluble in an aqueous alkaline developing solutionregardless of whether the acid generated by the actinic radiation isdeactivated or not and consequently the problem of substrate dependencecan completely be solved.

(in case where the acid labile group is 1-ethoxyethyl group).

The present invention is concerned an invention which can solvecompletely footing, etc., observed in using a positive tone resist,which is caused by deactivation of an acid generated by an actinicradiation around the surface area of a substrate in case of using so-farknown chemically-amplified resist composition to a specific substrate,particularly to a basic substrate (e.g. SiN, TiN, SiON, a basic organicanti-reflective film, etc.). Further, the present invention can solvecompletely the problem of substrate dependence essentially common to allchemically-amplified resist compositions, and thus the present inventioncan be used to a chemically-amplified resist composition not only forKrF excimer laser but also for ArF excimer laser, electron beam andothers (regardless of positive tone or negative tone).

In the following, the present invention is explained in detailsreferring to Examples and Comparative examples, and the presentinvention is not limited thereto by any means.

A part of the polymers and the acid generators used in the Examples andControl examples were synthesized according to the methods disclosedJapanese Patent Publication-Kokai-Nos 211258/1992, 210960/1992,249682/1993; 194472/1993, 53621/1998, etc.

EXAMPLE 1

A resist composition having the following ingredients was prepared:

poly(p-1-ethoxyethoxystyrene/ 4.5 gp-tert-butoxystyrene/p-hydroxystyrene) [constitutional ratio = 30:10:60,Mw 20000, Mw/Mn = 1.85] bis(cyclohexylsulfonyl)diazomethane 0.3 gbis(p-toluenesulfonyl)diazomethane 0.15 g tri-n-butylamine 0.05 g ethyllactate 3.0 g propyleneglycol monomethylether acetate 22.0 g

The above mixed solution was filtrated through a filter of 0.2 μm togive a resist composition, and a pattern was formed as follows.

The above resist composition was spin-coated on a silicon substratesurface, followed by pre-baking at 90° C. for 90 seconds on a hot plateto give a resist film of 0.7 μm thick. Then, the resist film wasselectively exposed to KrF excimer laser (λ=248.4 nm, NA 0.55) through amask, followed by post-baking at 105° C. for 90 seconds on a hot plate.The resultant was developed by a paddle method with an aqueous alkalinedeveloping solution (a 2.38% aqueous solution of tetramethylammoniumhydroxide) to dissolve 0.20 μm line and space (hereinafter, abbreviatedas L & S) pattern having a rectangular shape without footing at a doseof 32 mJ/cm². There was found no peeling off upon development. A coatinghomogeneity was good such as deviation of film thickness on the wholesurface of wafer upon film formation being ±10 Å. Further, when the samepattern formation as above was conducted by using the same compositionafter storage at 23° C. for 3 months, a 0.20 μm L & S pattern having arectangular shape without footing was obtained at a dose of 32 mJ/cm².

EXAMPLE 2

A spin-coating was conducted on a SiN substrate surface with the use ofthe same resist composition as in Example 1 so as to conduct a patternformation, whereupon 0.20 μm L & S pattern having a rectangular shapewithout footing as illustrated in FIG. 1 was obtained at a dose of 44mJ/cm². No peeling-off was observed.

EXAMPLE 3

A spin coating was conducted on a TiN substrate surface with the use ofthe same resist composition as Example 1 after the same manner as inExample 1, whereupon 0.20 μm L & S pattern having a rectangular shapewithout footing as illustrated in FIG. 1 was obtained at a dose of 40mJ/cm². No peeling-off was observed.

EXAMPLE 4

A spin coating was conducted on a SiON substrate surface with the use ofthe same resist composition as Example 1 after the same manner as inExample 1, whereupon 0.20 μm L & S pattern having a rectangular shapewithout footing as illustrated in FIG. 1 was obtained at a dose of 44mJ/cm². No peeling-off was observed.

EXAMPLE 5

A spin coating was conducted on a BPSG substrate surface with the use ofthe same resist composition as Example 1 after the same manner as inExample 1, whereupon 0.20 μm L & S pattern having a rectangular shapewithout footing as illustrated in FIG. 1 was obtained at a dose of 33mJ/cm². No peeling-off was observed.

EXAMPLES 6 TO 8

Resist compositions in Table 1 were prepared.

TABLE 1 E poly (p-1-ethoxyethoxystyrene/p-hydroxystyrene/ 4.5 g xtert-butyl methacrylate) m [constitutional ratio = 32:58:10, Mw 11000, pMw/Mn = 1.70] 6 bis(1,1-dimemthylethylsulfonyl)diazomethane 0.3 gtetra-n-butylammonium hydroxide 0.03 g methyl glycolate 1.5 gpropyleneglycol monomethylether acetate 23.7 g Epoly(p-1-ethoxyethoxystyrene/p-tert- 4.5 g xbutoxycarbonyloxystyrene/p-hydroxystyrene) p [constitutional ratio =30:62.8:8, Mw 10300, 7 Mw/Mn = 1.05] bis(cyclohexylsulfonyl)diazomethane0.3 g diphenyl-p-tolylsulfonium/p-toluenesulfonate 0.1 g triethylamine0.05 g ethyl glycolate 1.5 g propyleneglycol monomethylether acetate23.5 g E poly(p-tert-butoxystyrene/p-hydroxystyrene) 4.0 g x[constitutional ratio = 15:85, Mw 13500, p Mw/Mn = 1.40] 83,4-dihydro-4-(2,4-ditetrahydropyranyloxy- 1.0 gphenyl)-7-tetrahydropyranyloxy-2,2,4- trimethyl-2H-benzo-1-pyranebis(1-methylethylsulfonyl)diazomethane 0.3 gtriphenylsulfonium/p-toluenesulfonate 0.1 g tri-n-octylamine 0.05 gethyl 2-hydroxybutyrate 3.0 g propyleneglycol monomethylether acetate20.7 g

Pattern formation was conducted after the same manner as in Examples 1to 4. The result is shown in Table 2.

TABLE 2 silicon SiN TiN SiON substrate substrate substrate substrate Edose 36 mJ/cm² 50 mJ/cm² 45 mJ/cm² 50 mJ/cm² x dissolution 0.20 μm 0.20μm 0.20 μm 0.20 μm p L & S L & S L & S L & S 6 form rectangularrectangular rectangular rectangular no footing no footing no footing nofooting E dose 26 mJ/cm² 36 mJ/cm² 33 mJ/cm² 38 mJ/cm² x dissolution0.20 μm 0.20 μm 0.20 μm 0.20 μm p L & S L & S L & S L & S 7 formrectangular rectangular rectangular rectangular no footing no footing nofooting no footing E dose 26 mJ/cm² 35 mJ/cm² 32 mJ/cm² 36 mJ/cm² xdissolution 0.20 μm 0.20 μm 0.20 μm 0.20 μm p L & S L & S L & S L & S 8form rectangular rectangular rectangular rectangular no footing nofooting no footing no footing

A coating homogeneity in case of film formation on a silicon substrateusing the resist compositions of Examples 6 to 8 was good such asdeviation of film thickness on the whole surface of wafer upon filmformation being ±10 Å. Further, when the same pattern formation as abovewas conducted by using the same composition after storage at 23° C. for3 months, there was found no change in sensitivity, dissolution andshape.

EXAMPLE 9

A resist composition having the following ingredients was prepared:

poly(p-1-cyclohexyloxyethoxystyrene/ 2.5 gp-tert-butoxycarbonyloxystyrene/p-hydroxystyrene) [constitutional ratio= 25:10:65, Mw 18700, Mw/Mn = 1.11]poly(p-1-ethoxyethoxystyrene/p-hydroxystyrene) 2.0 g [constitutionalratio = 36:64, Mw 17500, Mw/Mn = 1.15]bis(cyclohexylsulfonyl)diazomethane 0.25 gdiphenyl-p-tolylsulfonium/p-toluenesulfonate 0.1 g dicyclohexylamine0.05 g ethyl 3-hydroxybutyrate 8.8 g propyleneglycol monomethyletheracetate 16.3 g

The above mixed solution was filtrated through a filter of 0.2 μm togive a resist composition and the above resist composition wasspin-coated on a silicon substrate surface, followed by conducting apattern formation after the same manner as in Example 1 to give 0.20 μmL & S pattern having a rectangular shape without footing at a dose of 28mJ/cm². There was found no peeling off in the inner surface of a waferupon development. A coating homogeneity was good such as deviation offilm thickness in the inner surface of a wafer upon film formation being±10 Å. Further, when the same pattern formation as above was conductedafter the same manner as in Example 1 with the use of the compositionafter storage at 23° C. for 3 months, a 0.20 μm L & S pattern having arectangular shape without footing was obtained at a dose of 28 mJ/cm².

EXAMPLE 10

A spin-coating was conducted on a TiN substrate surface with the use ofthe resist composition described in Example 9, followed by conducting apattern formation after the same manner as in Example 1 to give 0.20 μmL & S pattern having a rectangular shape without footing at a dose of 35mJ/cm². There was found no peeling-off.

EXAMPLE 11

A spin-coating was conducted on a SiON substrate surface with the use ofthe resist composition described in Example 9, followed by conducting apattern formation after the same manner as in Example 1 to give 0.20 μmL & S pattern having a rectangular shape without footing at a dose of 39mJ/cm². There was found no peeling-off.

EXAMPLE 12

An anti-reflective coating (DUV-32, manufactured by Brewer Science) wasspin-coated on a silicon substrate surface, followed by heating at 200°C. for 60 seconds on a hot plate to give an anti-reflective film. Aspin-coating was conducted on the surface of the anti-reflective filmusing the resist composition described in Example 9, followed byconducting a pattern formation after the same manner as in Example 1 togive 0.20 μm L & S pattern having a rectangular shape without footing ata dose of 32 mJ/cm². There was found no peeling-off.

EXAMPLE 13

A resist composition having the following ingredients was prepared:

poly(p-1-ethoxyethoxystyrene/ 4.0 g cyclohexylacrylate/p-hydroxystyrene) [constitutional ratio = 30:10:60, Mw 17500,Mw/Mn = 1.65] poly (p-1-ethoxyethoxystyrene/p-hydroxystyrene) 0.5 g[constitutional ratio = 36:64, Mw 17500, Mw/Mn = 1.15]bis(1,1-dimethylethylsulfonyl)diazomethane 0.25 gdiphenyl-p-tolylsulonium/p-toluenesulfonate 0.1 g tri-n-octylamine 0.05g ethyl 3-hydroxybutyrate 4.0 g propyleneglycol monomethylether acetate21.0 g

The above mixed solution was filtrated through a filter of 0.2 μm togive a resist composition, and the resist composition was spin-coated ona silicon substrate surface, followed by conducting a pattern formationby the same manner as in Example 1 to give 0.20 μm L & S pattern havinga rectangular shape without footing at a dose of 30 mJ/cm². There wasfound no peeling off in the inner surface of a wafer upon development. Acoating homogeneity was good such as deviation of film thickness in theinner surface of a wafer upon film formation being ±10 Å. Further, whenthe same pattern formation as above was conducted after the same manneras in Example 1 with the use of the composition after storage at 23° C.for 3 months, a 0.20 μm L & S pattern having a rectangular shape withoutfooting was obtained at a dose of 30 mJ/cm².

EXAMPLE 14

A spin-coating was conducted on a TiN substrate surface with the use ofthe resist composition described in Example 13, followed by conducting apattern formation after the same manner as in Example 1 to give a 0.20μm L & S pattern having a rectangular shape without footing at a dose of38 mJ/cm². There was found no peeling-off.

EXAMPLE 15

A spin-coating was conducted on a SiON substrate surface with the use ofthe resist composition described in Example 13, followed by conducting apattern formation after the same manner as in Example 1 to give a 0.20μm L & S pattern having a rectangular shape without footing at a dose of43 mJ/cm². There was found no peeling-off.

EXAMPLE 16

A spin-coating was conducted on an anti-reflective film formed by amethod of Example 12 with the use of the resist composition described inExample 13, followed by conducting a pattern formation after the samemanner as in Example 1 to give 0.20 μm L & S pattern having arectangular shape without footing at a dose of 34 mJ/cm². There wasfound no peeling-off.

EXAMPLE 17

A resist composition having the following ingredients was prepared

poly(p-1-ethoxyethoxystyrene/p-hydroxystyrene) 4.5 g [constitutionalratio = 15:85, Mw 2600, Mw/Mn = 1.05]2,4,6-tris-(methoxymethyl)amino-1,3,5-s-triazine 1.3 gbis(cyclohexylsulfonyl)diazomethane 0.25 gdiphenyl-p-tolylsulonium/perfluorooctanesulfonate 0.1 g tri-n-octylamine0.05 g ethyl 3-hydroxybutyrate 5.0 g propyleneglycol monomethyletheracetate 20.5 g

The above mixed solution was filtrated through a filter of 0.2 μm togive a resist composition, and the resist composition was spin-coated ona silicon substrate surface, followed by conducting a pattern formationby the same manner as in Example 1 to give 0.20 μm L & S negativepattern having a rectangular shape without under-cut at a dose of 24mJ/cm². There was found no peeling off in the inner surface of a waferupon development. A coating homogeneity was good such as deviation offilm thickness in the inner surface of a wafer upon film formation being±10 Å. Further, when the same pattern formation as above was conductedafter the same manner as in Example 1 with the use of the compositionafter storage at 23° C. for 3 months, a 0.20 μm L & S pattern having arectangular shape without footing was obtained at a dose of 24 mJ/cm².

EXAMPLE 18

A spin-coating was conducted on a SiON substrate surface with the use ofthe resist composition described in Example 17, followed by conducting apattern formation after the same manner as in Example 1 to give a 0.20μm L & S negative pattern having a rectangular shape without under-cutat a dose of 43 mJ/cm². There was found no peeling-off in the innersurface of wafer.

EXAMPLE 19

A resist composition having the following ingredients was prepared:

poly(p-1-cyclohexyloxyethoxystyrene/ 2.5 gp-tert-butoxycarbonyloxystyrene/p-hydroxystyrene) [constitutional ratio= 25:10:65, Mw 18700, Mw/Mn = 1.11]poly(p-1-ethoxyethoxystyrene/p-hydroxystyrene) 2.0 g [constitutionalratio = 36:64, Mw 17500, Mw/Mn = 1.15]bis(1,1-dimethylethylsulfonyl)diazomethane 0.25 gdiphenyl-p-tolylsulonium/p-toluenesulfonate 0.1 gdicyclohexylmethylamine 0.05 g ethyl 3-hydroxybutyrate 1.5 g ethyllactate 1.5 g propyleneglycol monomethylether acetate 22.1 g

The above mixed solution was filtrated through a filter of 0.2 μm togive a resist composition, and the resist composition was spin-coated ona silicon substrate surface, followed by conducting a pattern formationby the same manner as in Example 1 to give 0.20 μm L & S negativepattern having a rectangular shape without footing at a dose of 30mJ/cm². There was found no peeling off in the inner surface of a waferupon development. A coating homogeneity was good such as deviation offilm thickness on the inner surface of a wafer upon film formation being±10 Å. Further, when the same pattern formation as above was conductedafter the same manner as in Example 1 with the use of the compositionafter storage at 23° C. for 3 months, a 0.20 μm L & S pattern having arectangular shape without footing was obtained at a dose of 30 mJ/cm².

EXAMPLE 20

A spin-coating was conducted on a TiN substrate surface with the use ofthe resist composition described in Example 19, followed by conducting apattern formation after the same manner as in Example 1 to give a 0.20μm L & S pattern having a rectangular shape without footing at a dose of40 mJ/cm². There was found no peeling-off.

EXAMPLE 21

A spin-coating was conducted on a SiON substrate surface with the use ofthe resist composition described in Example 19, followed by conducting apattern formation after the same manner as in Example 1 to give a 0.20μm L & S pattern having a rectangular shape without footing at a dose of44 mJ/cm². There was found no peeling-off.

EXAMPLE 22

A spin-coating was conducted on an anti-reflective film formed by amethod of Example 12 with the use of the resist composition described inExample 19, followed by conducting a pattern formation after the samemanner as in Example 1 to give 0.20 μm L & S pattern having arectangular shape without footing at a dose of 36 mJ/cm². There wasfound no peeling-off.

Comparative Example 1

A resist composition having the following ingredients was prepared

poly(p-1-ethoxyethoxystyrene/ 4.5 gp-tert-butoxystyrene/p-hydroxystyrene) [constitutional ratio = 30:10:60,Mw 20000, Mw/Mn = 1.85] bis(cyclohexylsulfonyl)diazomethane 0.3 gbis(p-toluenesulfonyl)diazomethane 0.15 g tri-n-butylamine 0.05 gpropyleneglycol monomethylether acetate 25.0 g

With the use of the above resist composition, a pattern formation wasconducted on a silicon substrate after the same manner as in Example 1to dissolve 0.20 μm L & S pattern having a rectangular shape withoutfooting at a dose of 35 mJ/cm². A coating homogeneity was good such asdeviation of film thickness on the whole surface of wafer upon filmformation being ±10 Å and there was observed no peeling-off. Then, withthe use of the above resist composition, a pattern formation wasconducted on a TiN substrate surface after the same manner as in Example3, whereupon 0.20 μm L & S pattern was dissolved at a dose of 44 mJ/cm²but the pattern was, as shown in FIG. 2, such a bad one as beingaccompanied with a round shape on its upper part and large footing.Further, with the use of the above resist composition, a patternformation was conducted on a SiON substrate surface after the samemanner as in Example 4, whereupon 0.20 μm L & S pattern was dissolved ata dose of 50 mJ/cm² but the pattern was, as shown in FIG. 2, such a badone as being accompanied with a round shape on its upper part and largefooting.

Comparative Example 2

A resist composition having the following ingredients was prepared:

poly(p-1-ethoxyethoxystyrene/ 4.5 gp-tert-butoxystyrene/p-hydroxystyrene) [constitutional ratio = 30:10:60,Mw 20000, Mw/Mn = 1.85] bis(cyclohexylsulfonyl)diazomethane 0.3 gbis(p-toluenesulfonyl)diazomethane 0.15 g tri-n-butylamine 0.05 g ethyllactate 25.0 g

With the use of the above resist composition, a pattern formation wasconducted on a silicon substrate after the same manner as in Example 1to dissolve 0.20 μm L & S pattern having a rectangular shape withoutfooting at a dose of 35 mJ/cm². But a coating homogeneity was large suchas deviation of film thickness on the whole surface of wafer upon filmformation being ±20 Å and there was observed peeling-off in the innersurface of a wafer.

Further, with the use of the above resist composition, a patternformation was conducted on a TiN substrate surface after the same manneras in Example 3, whereupon 0.20 μm L & S pattern was dissolved at a doseof 44 mJ/cm². The pattern obtained has a rectangular shape withoutfooting, but there were observed many peeling-off in the inner surfaceof a wafer as shown in FIG. 3. Further, the above composition was storedat 23° C. for 3 months and a pattern was formed with the use of thusstored composition on a silicon substrate after the same manner as inExample 1, whereupon 0.22 μm L & S pattern was dissolved at a dose of 33mJ/cm² but the pattern was such a bad one as being accompanied with around shape on its upper part and footing.

Comparative Example 3

A resist composition having the following ingredients was prepared:

poly(p-1-ethoxyethoxystyrene/ 4.5 gp-tert-butoxystyrene/p-hydroxystyrene) [constitutional ratio = 30:10:60,Mw 20000, Mw/Mn = 1.85] bis(cyclohexylsulfonyl)diazomethane 0.3 gbis(p-toluenesulfonyl)diazomethane 0.15 g tri-n-butylamine 0.05 gsalicylic acid 0.3 g propyleneglycol monomethylether acetate 25.0 g

With the use of the above resist composition, a pattern formation wasconducted on a TiN substrate after the same manner as in Example 3 todissolve 0.20 μm L & S pattern at a dose of 38 mJ/cm², but the patternwas, as shown in FIG. 2, such a bad one as being accompanied with around shape on its upper part and footing.

Comparative Example 4

A resist composition having the following ingredients was prepared

poly(p-1-ethoxyethoxystyrene/ 4.5 gp-tert-butoxystyrene/p-hydroxystyrene) [constitutional ratio = 30:10:60,Mw 20000, Mw/Mn = 1.85] bis(cyclohexylsulfonyl)diazomethane 0.3 gbis(p-toluenesulfonyl)diazomethane 0.15 g tri-n-butylamine 0.05 gdiphenolic acid 0.3 g propyleneglycol monomethylether acetate 25.0 g

With the use of the above resist composition, a pattern formation wasconducted on a TiN substrate after the same manner as in Example 3 todissolve 0.20 μm L & S pattern at a dose of 38 mJ/cm², but the patternwas, as shown in FIG. 2, such a bad one as being accompanied with around shape on its upper part and footing.

Comparative Example 5

A resist composition having the following ingredients was prepared:

poly(p-1-ethoxyethoxystyrene/ 4.5 gp-tert-butoxystyrene/p-hydroxystyrene) [constitutional ratio = 30:10:60,Mw 20000, Mw/Mn = 1.85] bis(cyclohexylsulfonyl)diazomethane 0.3 gbis(p-toluenesulfonyl)diazomethane 0.15 g tri-n-butylamine 0.05 gsuccinimide 0.3 g propyleneglycol monomethylether acetate 25.0 g

With the use of the above resist composition, a pattern formation wasconducted on a TiN substrate after the same manner as in Example 3 todissolve 0.20 μm L & S pattern at a dose of 38 mJ/cm², but the patternwas, as shown in FIG. 2, such a bad one as being accompanied with around shape on its upper part and footing.

Comparative Example 6

A resist composition having the following ingredients was prepared:

poly(p-1-ethoxyethoxystyrene/ 4.5 gp-tert-butoxystyrene/p-hydroxystyrene) [constitutional ratio = 30:10:60,Mw 20000, Mw/Mn = 1.85] bis(cyclohexylsulfonyl)diazomethane 0.3 gbis(p-toluenesulfonyl)diazomethane 0.15 g tri-n-butylamine 0.05 g ethyllactate 12.5 g propyleneglycol monomethylether acetate 12.5 g

With the use of the above resist composition, a pattern formation wasconducted on a silicon substrate after the same manner as in Example 1to dissolve 0.20 μm L & S pattern having a rectangular shape withoutfooting at a dose of 35 mJ/cm², but a coating homogeneity was large suchas deviation of film thickness in the inner surface of a wafer upon filmformation being ±20 Å and there was observed peeling-off in the innersurface of a wafer.

Further, with the use of the above resist composition, a patternformation was conducted on a TiN substrate surface after the same manneras in Example 3, whereupon 0.20 μm L & S pattern was dissolved at a doseof 44 mJ/cm². The pattern obtained has a rectangular shape withoutfooting, but there were observed many peeling-off in the inner surfaceof a wafer. Further, the above composition was stored at 23° C. for 3months and a pattern was formed with the use of thus stored compositionafter the same manner as Example 1, whereupon 0.22 μm L & S pattern wasdissolved at a dose of 33 mJ/cm² but the pattern was such a bad one asbeing accompanied with a round shape on its upper part and footing.

Comparative Example 7

A resist composition having the following ingredients was prepared:

poly(p-1-ethoxyethoxystyrene/ 4.5 gp-tert-butoxystyrene/p-hydroxystyrene) [constitutional ratio = 30:10:60,Mw 20000, Mw/Mn = 1.85] bis(cyclohexylsulfonyl)diazomethane 0.3 gbis(p-toluenesulfonyl)diazomethane 0.15 g tri-n-butylamine 0.05 g ethyllactate 0.12 g propyleneglycol monomethylether acetate 24.9 g

With the use of the above resist composition, a pattern formation wasconducted on a silicon substrate after the same manner as in Example 1to dissolve 0.20 μm L & S pattern having a rectangular shape withoutfooting at a dose of 35 mJ/cm². A coating homogeneity was good such asdeviation of film thickness in the inner surface of wafer upon filmformation being ±10 Å and there was observed no peeling-off in the innersurface of a wafer.

Then, with the use of the above resist composition, a pattern formationwas conducted on a TiN substrate surface after the same manner as inExample 3, whereupon 0.20 μm L & S pattern was dissolved at a dose of 44mJ/cm²0.20 μm L & S pattern was dissolved at a dose of 44 mJ/cm², butthe pattern was such a bad one as being accompanied with a round shapeon its upper part and footing. Further, with the use of the abovecomposition, a pattern formation was conducted on a SiON substrate aafter the same manner as in Example 4, whereupon 0.22 μm L & S patternwas dissolved at a dose of 50 mJ/cm² but the pattern was such a bad oneas being accompanied with a round shape on its upper part and footing.Still further, with the use of the above composition, a patternformation was conducted on an anti-reflection membrane formed by amethod in Example 12, whereupon 0.20 μm L & S pattern was dissolved at adose of 38 mJ/cm² but the pattern was such a bad one as beingaccompanied with a round shape on its upper part and a large footing.

As clear from the above-mentioned, when the compound (an agent forreducing substrate dependence) shown by the general formula [1] of thepresent invention is added to a chemically-amplified resist composition,it is possible to solve completely such a problem concerning substratedependence so far being encountered in a case of using knownchemically-amplified resist compositions as a pattern becoming badbecause of deactivation of an acid generated by an actinic radiationwhich is caused by the influence of a basic substance and watergenerated from various kinds of substrates, and therefore the desiredpattern formation can be formed without any problem on every kinds ofsubstrates.

The technology of the present invention can be satisfactorily applied toa chemically-amplified resist compositions not only for KrF excimerlaser, but also for ArF excimer laser which is expected to be put intoactual use in near future, for F2 excimer laser, electron beam, andother various kinds of chemically amplified resist compositions.Therefore, the present invention has high value for ultra-fine patternformation in semiconductor industries.

What is claimed is:
 1. A method for reducing substrate dependence of aresist composition, which comprises the steps of: incorporating into theresist composition, as an agent for reducing substrate dependence, acompound shown by the following general formula [1]:

 wherein R₄₁ is a hydrogen atom or a methyl group, R₄₂ is a hydrogenatom, a methyl group, an ethyl group or a phenyl group, R₄₃ is astraight chained, branched or cyclic alkyl group having 1 to 6 carbonatoms, and n is 0 or 1, wherein an amount of the compound to be used is0.5 to 30 wt % relative to the total amount of the resist composition,applying the resist composition to a special substrate being selectedfrom the group consisting of SiN, TiN, SiON, BPSG and a strong basicorganic anti-reflective film, wherein the resist composition is onecontaining a) a polymer which becomes soluble in an aqueous alkalinedeveloping solution by a chemical change by an action of an acid, b) anacid generator.
 2. A method for reducing substrate dependence of aresist composition as claimed in claim 1, wherein the polymer whichbecomes soluble in an aqueous alkaline developing solution by a chemicalchange by an action of an acid is a compound shown by the generalformula [2] or [3]:

wherein R and R₁ are independently a hydrogen atom or a methyl group, R₂and R₃ are independently a hydrogen atom, a lower alkyl group or an arylgroup, except for the case where R₂ and R₃ are both hydrogen atoms, andR₂ and R₃ may form together an alkylene ring; R₄ is a lower alkyl groupor an aralkyl group; R₅ is a cyano group, a carboxylic group which maybe esterified or a phenyl group which may be substituted; m and n′ are anatural number; and k is 0 or a natural number, provided that m>k;

wherein R₆ and R₂₁ are independently a hydrogen atom or a methyl group;R₇ is a hydrogen atom, a lower alkyl group, a lower alkoxy group, anacyloxy group, a 5- to 6-membered saturated heterocyclic oxy group or agroup shown by the formula of R₈O—CO—(CH₂)z—O— in which R₈ is an alkylgroup and z is 0 or a natural number; R₂₂ is a cyano group, a phenylgroup which may have a substituent or a carboxyl group which may beesterified; p and r are natural number; f is 0 or a natural number,provided that p>f; with the proviso that when R₇ is a hydrogen atom, alower alkyl group, a lower alkoxy group except for one which is easilychanged into a hydroxy group by an acid, an acyloxy group or a groupR₈O—CO—(CH₂)z—O— (in which R₈ and z have the same meaning as above)except for a case where R₈ is a group labile by an acid, R₂₂ is a phenylgroup having a substituent which is easily changed into a hydroxy groupor a group of —COOR₄₅ (in which R₄₅ is an alkyl group labile by an acid)and that when R₇ is an alkoxy group which is easily changed into ahydroxy group, a 5- to 6-membered saturated oxy group or a group ofR₈O—CO—(CH₂)z—O— (in which R₈ and z have the same meaning as above) inwhich R₈ is labile by an acid, R₂₂ is a cyano group, a phenyl groupwhich may have a substituent or a carboxyl group which may beesterified.
 3. A method for reducing substrate dependence of a resistcomposition as claimed in claim 1, wherein the polymer which becomessoluble in an aqueous alkaline developing solution by a chemical changeby an action of an acid is apoly(p-1-ethoxyethoxystyrene/styrene/p-hydroxystyrene/tert-butylacrylate) orpoly(p-1-ethoxyethoxystyrene/styrene/p-hydroxystyrene/tert-butylmethacrylate).
 4. A method for reducing substrate dependence of a resistcomposition as claimed in claim 1, wherein the acid generator is acompound represented by the general formula [8], [9], [11], [12], [13]and [15];

wherein R₉ and R₁₀ are independently an alkyl group or a haloalkyl groupand A′ is a sulfonyl group or a carbonyl group;

wherein R₁₁ is a hydrogen atom, a halogen atom, an alkyl group, analkoxy group or a haloalkyl group, and R₁₂ is an alkyl group, ahaloalkyl group or a group shown by the following general formula [10]:

wherein R₁₃ is a hydrogen atom, a halogen atom, an alkyl group, analkoxy group or a haloalkyl group, and q is 0 or an integer of 1 to 3;

wherein R₁₄ is a hydrogen atom, a halogen atom, an alkyl group or atrifluoromethyl group and R₁₅ is an alkyl group, an aralkyl group, analkoxy group, a phenyl group or a tolyl group;

wherein R₁₆ is an alkyl group, a phenyl group, a substituted phenylgroup or an aralkyl group, R₁₇ and R₁₈ are independently a hydrogenatom, an alkyl group, a phenyl group, a substituted phenyl group or anaralkyl group, and R₁₉ is a fluoroalkyl group, a trifluoromethylphenylgroup, a methyl group or tolyl group;

wherein R₂₉ is an alkyl group, a fluoroalkyl group, a phenyl group, asubstituted phenyl group or an aralkyl group, Q′ is a sulfonyl group ora carbonyl group, R₃₀ and R₃₁ are independently a hydrogen atom, amethyl group, a methoxy group, a nitro group, a cyano group, a hydroxygroup or a group shown by the following general formula [14]:

wherein R₃₃ is an alkyl group, a fluoroalkyl group, a phenyl group, asubstituted phenyl group or an aralkyl group, Q′ is a sulfonyl group ora carbonyl group, and R₃₂ is a hydrogen atom, a methyl group or an ethylgroup;

wherein R₃₄ is an alkyl group, a fluoroalkyl group, a phenyl group, asubstituted phenyl group or an aralkyl group, R₃₅ is a hydrogen atom, amethyl group, a fluoroalkyl group, a methoxy group, a nitro group, acyano group, a hydroxy group or a group shown by the above generalformula [14].
 5. A method for reducing substrate dependence of a resistcomposition, which comprises the steps of: incorporating into the resistcomposition, as an agent for reducing substrate dependence, a compoundshown by the following general formula [1]:

 wherein R₄₁ is a hydrogen atom or a methyl group, R₄₂ is a hydrogenatom, a methyl group, an ethyl group or a phenyl group, R₄₃ is astraight chained, branched or cyclic alkyl group having 1 to 6 carbonatoms, and n is 0 or 1, wherein an amount of the compound to be used is0.5 to 30 wt % relative to the total amount of the resist composition,applying the resist composition to a special substrate being selectedfrom the group consisting of SiN, TiN, SiON, BPSG and a strong basicorganic anti-reflective film, wherein the resist composition is onecontaining a) a polymer soluble in an aqueous alkaline developingsolution, b) an acid generator, c) a cross-linking compound which canmake the polymer soluble in an aqueous alkaline developing solutionhardly soluble in an aqueous alkaline developing solution by a chemicalchange by an action of an acid.
 6. A method for reducing substratedependence of a resist composition as claimed in claim 5, wherein thepolymer soluble in an aqueous alkaline developing solution ispoly(p-hydroxystyrene), poly(styrene/p-hydroxystyrene) wherein the ratioof styrene units to p-hydroxystyrene units is limited to 4 or less:6 ormore, said ratio being hereinafter represented by 4↓:6↑,poly(p-tert-butoxystyrene/p-hydroxystyrene) wherein the ratio ofp-tert-butoxystyrene units to p-hydroxystyrene units is limited to2↓:8↑, poly(p-isopropoxystyrene/p-hydroxystyrene) wherein the ratio ofp-isopropoxystyrene units to p-hydroxystyrene units is limited to 2↓:8↑,poly(p-tetrahydropyranyloxystyrene/p-hydroxystyrene) wherein the ratioof p-tetrahydropyranyloxystyrene units to p-hydroxystyrene units islimited to 2↓:8↑, poly(p-tert-butoxycarbonyloxystyrene/p-hydroxystyrene)wherein the ratio of p-tert-butoxycarbonyloxystyrene units top-hydroxystyrene units is limited to 2↓:8↑,poly(p-1-ethoxyethoxystyrene/p-hydroxystyrene) wherein the ratio ofp-1-ethoxyethoxystyrene units to p-hydroxystyrene units is limited to2↓:8↑,poly(p-1-ethoxyethoxystyrene/p-tert-butoxystyrene/p-hydroxystyrene)wherein the ratio of the sum of p-1-ethoxyethoxystyrene units andp-tert-butoxystyrene units to p-hydroxystyrene units is limited to2↓:8↑, poly(p-1-ethoxyethoxystyrene/styrene/p-hydroxystyrene) whereinthe ratio of the sum of p-1-ethoxyethoxystyrene units and styrene unitsto p-hydroxystyrene units is limited to 2↓:8↑,poly(p-hydroxystyrene/styrene/tert-butyl acrylate) wherein the ratio ofp-hydroxystyrene units to the sum of styrene units and tert-butylacrylate units is limited to 7↑:3↓ orpoly(p-hydroxystyrene/styrene/tert-butyl methacrylate) wherein the ratioof p-hydroxystyrene units to the sum of styrene units and tert-butylmethacrylate units is limited to 7↑:3↓.
 7. A method for reducingsubstrate dependence of a resist composition as claimed in claim 5,wherein the acid generator is a compound represented by the generalformula (8), (9), (11), (12), (13) and (15);

wherein R₉ and R₁₀ are independently an alkyl group or a haloalkyl groupand A′ is a sulfonyl group or a carbonyl group;

wherein R₁₁ is a hydrogen atom, a halogen atom, an alkyl group, analkoxy group or a haloalkyl group, and R₁₂ is an alkyl group, ahaloalkyl group or a group shown by the following general formula (10):

wherein R₁₃ is a hydrogen atom, a halogen atom, an alkyl group, analkoxy group or a haloalkyl group, and q is 0 or an integer of 1 to 3;

wherein R₁₄ is a hydrogen atom, a halogen atom, an alkyl group or atrifluoromethyl group and R₁₅ is an alkyl group, an aralkyl group, analkoxy group, a phenyl group or a tolyl group;

wherein R₁₆ is an alkyl group, a phenyl group, a substituted phenylgroup or an aralkyl group, R₁₇ and R₁₈ are independently a hydrogenatom, an alkyl group, a phenyl group, a substituted phenyl group or anaralkyl group, and R₁₉ is a fluoroalkyl group, a trifluoromethylphenylgroup, a methyl group or a tolyl group;

wherein R₂₉ is an alkyl group, a fluoroalkyl group, a phenyl group, asubstituted phenyl group or an aralkyl group, Q′ is a sulfonyl group ora carbonyl group, R₃₀ and R₃₁ are independently a hydrogen atom, amethyl group, a methoxy group, a nitro group, a cyano group, a hydroxygroup or a group shown by the following general formula (14):

wherein R₃₃ is an alkyl group, a fluoroalkyl group, a phenyl group, asubstituted phenyl group or an aralkyl group, Q′ is a sulfonyl group ora carbonyl group, and R₃₂ is a hydrogen atom, a methyl group or an ethylgroup;

wherein R₃₄ is an alkyl group, a fluoroalkyl group, a phenyl group, asubstituted phenyl group or an aralkyl group, R₃₅ is a hydrogen atom, amethyl group, a fluoroalkyl group, a methoxy group, a nitro group, acyano group, a hydroxy group or a group shown by the above generalformula (14).
 8. A method for reducing substrate dependence of a resistcomposition as claimed in claim 5, wherein the cross-linking compound isone shown by the general formula [4];

wherein R₃₆ is an alkyl group, R₃₇ is a hydrogen atom or a group shownby the general formula [5]:

wherein R₃₆ has the same meaning as above, or one shown by the generalformula [6];

wherein R₃₈ is a hydrogen atom or an alkyl group, and R₃₉ is a hydrogenatom or a group shown by the general formula [7]:

wherein R₃₈ has the same meaning as above.
 9. A coated substratecomprising: a special substrate made of a material selected from thegroup consisting of SiN, TiN, SiON, BPSG and a strong basic organicanti-reflective film; and a resist film obtained by coating a resistcomposition on said substrate, said resist composition comprising: a) acompound shown by the following general formula [1]:

 wherein R₄₁ is a hydrogen atom or a methyl group, R₄₂ is a hydrogenatom, a methyl group, an ethyl group or a phenyl group, R₄₃ is astraight chained, branched or cyclic alkyl group having 1 to 6 carbonatoms, and n is 0 or 1, wherein an amount of the compound to be used is0.5 to 30 wt % relative to the total amount of the resist composition,b) a polymer which becomes soluble in an aqueous alkaline developingsolution by a chemical change by an action of an acid, and c) an acidgenerator; wherein the polymer which becomes soluble in an aqueousalkaline developing solution by a chemical change by an action of anacid is a compound shown by the general formula [2] or [3]:

 wherein R and R₁ are independently a hydrogen atom or a methyl group,R₂ and R₃ are independently a hydrogen atom, a lower alkyl group or anaryl group, except for the case where R₂ and R₃ are both hydrogen atoms,and R₂ and R₃ may form together an alkylene ring; R₄ is a lower alkylgroup or an aralkyl group; R₅ is a cyano group; a carboxylic group whichmay be esterified or a phenyl group which may be substituted; m and n′are a natural number; and k is 0 or a natural number provided that m>k;

 wherein R₆ and R₂₁ are independently a hydrogen atom or a methyl group;R₇ is a hydrogen atom, a lower alkyl group, a lower alkoxy group, anacyloxy group, a 5- or 6-membered saturated heterocyclic oxy group or agroup shown by the formula of R₈O—CO—(CH₂)z—O— in which R₈ is an alkylgroup or z is 0 or a natural number; R₂₂ is a cyano group, a phenylgroup which may have a substituent or a carboxyl group which may beesterified; p and r are natural number; f is 0 or a natural number,provided that p>f; with the proviso that when R₇ is a hydrogen atom, alower alkyl group, a lower alkoxy group except for one which is easilychanged into a hydroxy group by an acid, an acyloxy group or a groupR₈O—CO—(CH₂)z—O— (in which R₈ and z have the same meaning as above)except for a case where R₈ is a group labile by an acid, R₂₂ is a phenylgroup having a substituent which is easily changed into a hydroxy groupor a group of —COOR₄₅ (in which R₄₅ is an alkyl group labile by an acid)an that when R₇ is an alkoxy group which is easily changed into ahydroxy group, a 5- or 6-membered saturated oxy group or a group ofR₈O—CO—(CH₂)z—O— (in which R₈ and z have the same meaning as above) inwhich R₈ is labile by an acid, R₂₂ is a cyano group, a phenyl groupwhich may have a substituent or a carboxyl group which may beesterified.
 10. A coated substrate comprising: a special substrate madeof a material selected from the group consisting of SiN, TiN, SiON, BPSGand a strong basic organic anti-reflective film; and a resist filmobtained by coating a resist composition on said substrate, said resistcomposition comprising: a) a compound shown by the following generalformula [1]:

 wherein R₄₁ is a hydrogen atom or a methyl group, R₄₂ is a hydrogenatom, a methyl group, an ethyl group or a phenyl group, R₄₃ is astraight chained, branched or cyclic alkyl group having 1 to 6 carbonatoms, and n is 0 or 1, wherein an amount of the compound to be used is0.5 to 30 wt % relative to the total amount of the resist composition,b) a polymer which becomes soluble in an aqueous alkaline developingsolution by a chemical change by an action of an acid, and c) an acidgenerator; wherein the polymer which becomes soluble in an aqueousalkaline developing solution by a chemical change by an action of anacid is apoly(p-1-ethoxyethoxystyrene/styrene/p-hydroxystyrene/tert-butylacrylate) orpoly(p-1-ethoxyethoxystyrene/styrene/p-hydroxystyrene/tert-butylmethacrylate).
 11. A coated substrate comprising: a special substratemade of a material selected from the group consisting of SiN, TiN, SiON,BPSG and a strong basic organic anti-reflective film; and a resist filmobtained by coating a resist composition on said substrate, said resistcomposition comprising: a) a compound shown by the following generalformula [1]:

 wherein R₄₁ is a hydrogen atom or a methyl group, R₄₂ is a hydrogenatom, a methyl group, an ethyl group or a phenyl group, R₄₃ is astraight chained, branched or cyclic alkyl group having 1 to 6 carbonatoms, and n is 0 or 1, wherein an amount of the compound to be used is0.5 to 30 wt % relative to the total amount of the resist composition,b) a polymer which becomes soluble in an aqueous alkaline developingsolution by a chemical change by an action of an acid, and c) an acidgenerator;  wherein the acid generator is a compound represented by thegeneral formula [8], [9], [11], [12], [13] and [15];

 wherein R₉ and R₁₀ are independently an alkyl group or a haloalkylgroup and A′ is a sulfonyl group or a carbonyl group;

 wherein R₁₁ is a hydrogen atom, a halogen atom, an alkyl group, analkoxy group or a haloalkyl group, and R₁₂ is an alkyl group, ahaloalkyl group or a group shown by the following general formula [10]:

 wherein R₁₃ is a hydrogen atom, a halogen atom, an alkyl group, analkoxy group or a halogen group, and q is 0 or an integer of 1 to 3;

 wherein R₁₄ is a hydrogen atom, a halogen atom, an alkyl group or atrifluoromethyl group and R₁₅ is an alkyl group, an aralkyl group, analkoxy group, a phenyl group or a tolyl group;

 wherein R₁₆ is an alkyl group, a phenyl group, a substituted phenylgroup or an aralkyl group, R₁₇ and R₁₈ are independently a hydrogenatom, an alkyl group, a phenyl group, a substituted phenyl group or anaralkyl group, and R₁₉ is a fluoroalkyl group, a trifluoromethylphenylgroup, a methyl group or tolyl group;

 wherein R₂₉ is an alkyl group, a fluoroalkyl group, a phenyl group, asubstituted phenyl group or an aralkyl group, Q′ is a sulfonyl group ora carbonyl group, R₃₀ and R₃₁ are independently a hydrogen atom, amethyl group, a methoxy group, a nitro group, a cyano group, a hydroxygroup or a group shown by the following general formula [14]:

 wherein R₃₃ is an alkyl group, a fluoroalkyl group, a phenyl group, asubstituted phenyl group or an aralkyl group, Q′ is a sulfonyl group ora carbonyl group, and R₃₂ us a hydrogen atom, a methyl group or an ethylgroup;

 wherein R₃₄ is an alkyl group, a fluoroalkyl group, a phenyl group, asubstituted phenyl group or an aralkyl group, R₃₅ is a hydrogen atom, amethyl group, a fluoroalkyl group, a methoxy group, a nitro group, acyano group, a hydroxy group or a group shown by the above generalformula [14].
 12. A coated substrate comprising: a special substratemade of a material selected from the group consisting of SiN, TiN, SiON,BPSG and a strong basic organic anti-reflective film; and a resist filmobtained by coating a resist composition on said substrate, said resistcomposition comprising: a) a compound shown by the following generalformula [1]

 wherein R₄₁ is a hydrogen atom or a methyl group, R₄₂ is a hydrogenatom, a methyl group, an ethyl group or a phenyl group, R₄₃ is astraight chained, branched or cyclic alkyl group having 1 to 6 carbonatoms, and n is 0 or 1, wherein an amount of the compound to be used is0.5 to 30 wt % relative to the total amount of the resist composition,b) a polymer soluble in an aqueous alkaline developing solution, c) anacid generator, and d) a cross-linking compound which can make a polymerhardly soluble in an aqueous alkaline developing solution by a chemicalchange by an action of an acid.
 13. The coated substrate as claimed inclaim 12, wherein the compound shown by the general formula [1] ismethyl glycolate, ethyl glycolate, n-propyl glycolate, isopropylglycolate, n-butyl glycolate, isobutyl glycolate, tert-butyl glycolate,n-pentyl glycolate, isopentyl glycolate, n-hexyl glycolate, cyclohexylglycolate, methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate,n-propyl 3-hydroxypropionate, methyl 2-hydroxybutyrate, ethyl2-hydroxybutyrate, n-propyl 2-hydroxybutyrate, methyl2-hydroxyisobutyrate, ethyl 2-hydroxyisobutyrate, methyl3-hydroxybutyrate, ethyl 3-hydroxybutyrate, methyl 3-hydroxyvalerate,ethyl 3-hydroxyvalerate, methyl mandelate, ethyl mandelate, n-propylmandelate or isopropyl mandelate.
 14. The coated substrate as claimed inclaim 12, wherein the compound shown by the general formula [1] ismethyl glycolate, ethyl glycolate, methyl 2-hydroxybutyrate, ethyl2-hydroxybutyrate, methyl 3-hydroxybutyrate, ethyl 3-hydroxybutyrate,methyl mandelate or ethyl mandelate.
 15. The coated substrate as claimedin claim 12, wherein the compound shown by the general formula [1] thecompound is methyl glycolate, ethyl glycolate, methyl 3-hydroxybutyrate,ethyl 3-hydroxybutyrate or ethyl mandelate.
 16. The coated substrate asclaimed in claim 12, wherein the polymer soluble in an aqueous alkalinedeveloping solution is poly(p-hydroxystyrene),poly(styrene/p-hydroxystyrene) wherein the ratio of styrene units top-hydroxystyrene units is limited to 4 or less:6 or more, said ratiobeing hereinafter represented by 4↓:6↑,poly(p-tert-butoxystyrene/p-hydroxystyrene) wherein the ratio ofp-tert-butoxystyrene units to p-hydroxystyrene units is limited to2↓:8↑, poly(p-isopropoxystyrene/p-hydroxystyrene) wherein the ratio ofp-isopropoxystyrene units to p-hydroxystyrene units is limited to 2↓:8↑,poly(p-tetrahydropyranyloxystyrene/p-hydroxystyrene) wherein the ratioof p-tetrahydropyranyloxystyrene units to p-hydroxystyrene units islimited to 2↓:8↑, poly(p-tert-butoxycarbonyloxystyrene/p-hydroxystyrene)wherein the ratio of p-tert-butoxycarbonyloxystyrene units top-hydroxystyrene units is limited to 2↓:8↑,poly(p-1-ethoxyethoxystyrene/p-hydroxystyrene) wherein the ratio ofp-1-ethoxyethoxystyrene units to p-hydroxystyrene units is limited to2↓:8↑,poly(p-1-ethoxyethoxystyrene/p-tert-butoxystyrene/p-hydroxystyrene)wherein the ratio of the sum of p-1-ethoxyethoxystyrene units andp-tert-butoxystyrene units to p-hydroxystyrene units is limited to2↓:8↑, poly(p-1-ethoxyethoxystyrene/styrene/p-hydroxystyrene) whereinthe ratio of the sum of p-1-ethoxyethoxystyrene units and styrene unitsto p-hydroxystyrene units is limited to 2↓:8↑,poly(p-hydroxystyrene/styrene/tert-butyl acrylate) wherein the ratio ofp-hydroxystyrene units to the sum of styrene units and tert-butylacrylate units is limited to 7↑:3↓ orpoly(p-hydroxystyrene/styrene/tert-butyl methacrylate) wherein the ratioof p-hydroxystyrene units to the sum of styrene units and tert-butylmethacrylate units is limited to 7↑:3↓.
 17. The coated substrate asclaimed in claim 12, wherein the acid generator is a compoundrepresented by the general formula [8], [9], [11], [12], [13] and [15];

wherein R₉ and R₁₀ are independently an alkyl group or a haloalkyl groupand A′ is a sulfonyl group or a carbonyl group;

wherein R₁₁ is a hydrogen atom, a halogen atom, an alkyl group, analkoxy group or a haloalkyl group, and R₁₂ is an alkyl group, ahaloalkyl group or a group shown by the following general formula [10]:

wherein R₁₃ is a hydrogen atom, a halogen atom, an alkyl group, analkoxy group or a haloalkyl group, and q is 0 or an integer of 1 to 3;

wherein R₁₄ is a hydrogen atom, a halogen atom, an alkyl group or atrifluoromethyl group and R₁₅ is an alkyl group, an aralkyl group, analkoxy group, a phenyl group or a tolyl group;

wherein R₁₆ is an alkyl group, a phenyl group, a substituted phenylgroup or an aralkyl group, R₁₇ and R₁₈ are independently a hydrogenatom, an alkyl group, a phenyl group, a substituted phenyl group or anaralkyl group, and R₁₉ is a fluoroalkyl group, a trifluoromethylphenylgroup, a methyl group or tolyl group;

wherein R₂₉ is an alkyl group, a fluoroalkyl group, a phenyl group, asubstituted phenyl group or an aralkyl group, Q′ is a sulfonyl group ora carbonyl group, R₃₀ and R₃₁ are independently a hydrogen atom, amethyl group, a methoxy group, a nitro group, a cyano group, a hydroxygroup or a group shown by the following general formula [14]:

wherein R₃₃ is an alkyl group, a fluoroalkyl group, a phenyl group, asubstituted phenyl group or an aralkyl group, Q′ is a sulfonyl group ora carbonyl group, and R₃₂ is a hydrogen atom, a methyl group or an ethylgroup;

wherein R₃₄ is an alkyl group, a fluoroalkyl group, a phenyl group, asubstituted phenyl group or an aralkyl group, R₃₅ is a hydrogen atom, amethyl group, a fluoroalkyl group, a methoxy group, a nitro group, acyano group, a hydroxy group or a group shown by the above generalformula [14].
 18. The coated substrate as claimed in claim 12, whereinthe cross-linking compound is one shown by the general formula [4];

wherein R₃₆ is an alkyl group, R₃₇ is a hydrogen atom or a group shownby the general formula [5]:

wherein R₃₆ has the same meaning as above, or one shown by the generalformula [6];

wherein R₃₈ is a hydrogen atom or an alkyl group, and R₃₉ is a hydrogenatom or a group shown by the general formula [7]:

wherein R₃₈ has the same meaning as above.
 19. A resist composition fora special substrate being selected from the group consisting of SiN,TiN, SiON, BPSG and a strong basic organic anti-reflective film, whichcomprises; a) a compound selected from the group consisting of methylglycolate, ethyl glycolate, n-propyl glycolate, isopropyl glycolate,n-butyl glycolate, isobutyl glycolate, tert-butyl glycolate, n-pentylglycolate, isopentyl glycolate, n-hexyl glycolate, cyclohexyl glycolate,methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, n-propyl3-hydroxypropionate, methyl 2-hydroxybutyrate, ethyl 2-hydroxybutyrate,n-propyl 2-hydroxybutyrate, methyl 2-hydroxyisobutyrate, ethyl2-hydroxyisobutyrate, methyl 3-hydroxybutyrate, ethyl 3-hydroxybutyrate,methyl 3-hydroxyvalerate, ethyl 3-hydroxyvalerate, methyl mandelate,ethyl mandelate, n-propyl mandelate and isopropyl mandelate, b) apolymer which becomes soluble in an aqueous alkaline developing solutionby a chemical change by an action of an acid, and c) an acid generator.20. The resist composition as claimed in claim 19, wherein an amount ofthe compound to be used is 0.5 to 30 wt % relative to the total amountof the resist composition.
 21. The resist composition as claimed inclaim 19, wherein the compound is methyl glycolate, ethyl glycolate,methyl 2-hydroxybutyrate, ethyl 2-hydroxybutyrate, methyl3-hydroxybutyrate, ethyl 3-hydroxybutyrate, methyl mandelate or ethylmandelate.
 22. The resist composition as claimed in claim 19, whereinthe compound is methyl glycolate, ethyl glycolate, methyl3-hydroxybutyrate, ethyl 3-hydroxybutyrate or ethyl mandelate.
 23. Theresist composition as claimed in claim 19, wherein the polymer whichbecomes soluble in an aqueous alkaline developing solution by a chemicalchange by an action of an acid is a compound shown by the generalformula [2] or [3]:

wherein R and R₁ are independently a hydrogen atom or a methyl group, R₂and R₃ are independently a hydrogen atom, a lower alkyl group or an arylgroup, except for the case where R₂ and R₃ are both hydrogen atoms, andR₂ and R₃ may form together an alkylene ring; R₄ is a lower alkyl groupor an aralkyl group; R₅ is a cyano group, a carboxylic group which maybe esterified or a phenyl group which may be substituted; m and n′ are anatural number; and k is 0 or a natural number, provided that m>k;

wherein R₆ and R₂₁ are independently a hydrogen atom or a methyl group;R₇ is a hydrogen atom, a lower alkyl group, a lower alkoxy group, anacyloxy group, a 5- to 6-membered saturated heterocyclic oxy group or agroup shown by the formula of R₈O—CO—(CH₂)z—O— in which R₈ is an alkylgroup and z is 0 or a natural number; R₂₂ is a cyano group, a phenylgroup which may have a substituent or a carboxyl group which may beesterified; p and r are natural number; f is 0 or a natural number,provided that p>f; with the proviso that when R₇ is a hydrogen atom, alower alkyl group, a lower alkoxy group except for one which is easilychanged into a hydroxy group by an acid, an acyloxy group or a groupR₈O—CO—(CH₂)z—O— (in which R₈ and z have the same meaning as above)except for a case where R₈ is a group labile by an acid, R₂₂ is a phenylgroup having a substituent which is easily changed into a hydroxy groupor a group of —COOR₄₅ (in which R₄₅ is an alkyl group labile by an acid)and that when R₇ is an alkoxy group which is easily changed into ahydroxy group, a 5- to 6-membered saturated oxy group or a group ofR₈O—CO—(CH₂)z—O— (in which R₈ and z have the same meaning as above) inwhich R₈ is labile by an acid, R₂₂ is a cyano group, a phenyl groupwhich may have a substituent or a carboxyl group which may beesterified.
 24. The resist composition as claimed in claim 19, whereinthe polymer which becomes soluble in an aqueous alkaline developingsolution by a chemical change by an action of an acid is apoly(p-1-ethoxyethoxystyrene/styrene/p-hydroxystyrene/tert-butylacrylate) orpoly(p-1-ethoxyethoxystyrene/styrene/p-hydroxystyrene/tert-butylmethacrylate).
 25. The resist composition as claimed in claim 19,wherein the acid generator is a compound represented by the generalformula [8], [9], [11], [12], [13] and [15];

wherein R₉ and R₁₀ are independently an alkyl group or a haloalkyl groupand A′ is a sulfonyl group or a carbonyl group;

wherein R₁₁ is a hydrogen atom, a halogen atom, an alkyl group, analkoxy group or a haloalkyl group, and R₁₂ is an alkyl group, ahaloalkyl group or a group shown by the following general formula [10]:

wherein R₁₃ is a hydrogen atom, a halogen atom, an alkyl group, analkoxy group or a haloalkyl group, and q is 0 or an integer of 1 to 3;

wherein R₁₄ is a hydrogen atom, a halogen atom, an alkyl group or atrifluoromethyl group and R₁₅ is an alkyl group, an aralkyl group, analkoxy group, a phenyl group or a tolyl group;

wherein R₁₆ is an alkyl group, a phenyl group, a substituted phenylgroup or an aralkyl group, R₁₇ and R₁₈ are independently a hydrogenatom, an alkyl group, a phenyl group, a substituted phenyl group or anaralkyl group, and R₁₉ is a fluoroalkyl group, a trifluoromethylphenylgroup, a methyl group or tolyl group;

wherein R₂₉ is an alkyl group, a fluoroalkyl group, a phenyl group, asubstituted phenyl group or an aralkyl group, Q′ is a sulfonyl group ora carbonyl group, R₃₀ and R₃₁ are independently a hydrogen atom, amethyl group, a methoxy group, a nitro group, a cyano group, a hydroxygroup or a group shown by the following general formula [14]:

wherein R₃₃ is an alkyl group, a fluoroalkyl group, a phenyl group, asubstituted phenyl group or an aralkyl group, Q′ is a sulfonyl group ora carbonyl group, and R₃₂ is a hydrogen atom, a methyl group or an ethylgroup;

wherein R₃₄ is an alkyl group, a fluoroalkyl group, a phenyl group, asubstituted phenyl group or an aralkyl group, R₃₅ is a hydrogen atom, amethyl group, a fluoroalkyl group, a methoxy group, a nitro group, acyano group, a hydroxy group or a group shown by the above generalformula [14].
 26. A resist composition for a special substrate beingselected from the group consisting of SiN, TiN, SiON, BPSG and a strongbasic organic anti-reflective film, which comprises; a) a compoundselected from the group consisting of methyl glycolate, ethyl glycolate,n-propyl glycolate, isopropyl glycolate, n-butyl glycolate, isobutylglycolate, tert-butyl glycolate, n-pentyl glycolate, isopentylglycolate, n-hexyl glycolate, cyclohexyl glycolate, methyl3-hydroxypropionate, ethyl 3-hydroxypropionate, n-propyl3-hydroxypropionate, methyl 2-hydroxybutyrate, ethyl 2-hydroxybutyrate,n-propyl 2-hydroxybutyrate, methyl 2-hydroxyisobutyrate, ethyl2-hydroxyisobutyrate, methyl 3-hydroxybutyrate, ethyl 3-hydroxybutyrate,methyl 3-hydroxyvalerate, ethyl 3-hydroxyvalerate, methyl mandelate,ethyl mandelate, n-propyl mandelate and isopropyl mandelate, b) apolymer soluble in an aqueous alkaline developing solution, c) an acidgenerator, and d) a compound which becomes soluble in an aqueousalkaline developing solution by a chemical change by an action of anacid.
 27. The resist composition as claimed in claim 26, wherein anamount of the compound to be used is 0.5 to 30 wt % relative to thetotal amount of the resist composition.
 28. The resist composition asclaimed in claim 26, wherein the compound is methyl glycolate, ethylglycolate, methyl 2-hydroxybutyrate, ethyl 2-hydroxybutyrate, methyl3-hydroxybutyrate, ethyl 3-hydroxybutyrate, methyl mandelate or ethylmandelate.
 29. The resist composition as claimed in claim 26, whereinthe compound is methyl glycolate, ethyl glycolate, methyl3-hydroxybutyrate, ethyl 3-hydroxybutyrate, or ethyl mandelate.
 30. Theresist composition as claimed in claim 26, wherein the polymer solublein an aqueous alkaline developing solution is poly(p-hydroxystyrene),poly(styrene/p-hydroxystyrene) wherein the ratio of styrene units top-hydroxystyrene units is limited to 4 or less:6 or more, said ratiobeing hereinafter represented by 4↓:6↑,poly(p-tert-butoxystyrene/p-hydroxystyrene) wherein the ratio ofp-tert-butoxystyrene units to p-hydroxystyrene units is limited to2↓:8↑, poly(p-isopropoxystyrene/p-hydroxystyrene) wherein the ratio ofp-isopropoxystyrene units to p-hydroxystyrene units is limited to 2↓:8↑,poly(p-tetrahydropyranyloxystyrene/p-hydroxystyrene) wherein the ratioof p-tetrahydropyranyloxystyrene units to p-hydroxystyrene units islimited to 2↓:8↑, poly(p-tert-butoxycarbonyloxystyrene/p-hydroxystyrene)wherein the ratio of p-tert-butoxycarbonyloxystyrene units top-hydroxystyrene units is limited to 2↓:8↑,poly(p-1-ethoxyethoxystyrene/p-hydroxystyrene) wherein the ratio ofp-1-ethoxyethoxystyrene units to p-hydroxystyrene units is limited to2↓:8↑,poly(p-1-ethoxyethoxystyrene/p-tert-butoxystyrene/p-hydroxystyrene)wherein the ratio of the sum of p-1-ethoxyethoxystyrene units andp-tert-butoxystyrene units to p-hydroxystyrene units is limited to2↓:8↑, poly(p-1-ethoxyethoxystyrene/styrene/p-hydroxystyrene) whereinthe ratio of the sum of p-1-ethoxyethoxystyrene units and styrene unitsto p-hydroxystyrene units is limited to 2↓:8↑,poly(p-hydroxystyrene/styrene/tert-butyl acrylate) wherein the ratio ofp-hydroxystyrene units to the sum of styrene units and tert-butylacrylate units is limited to 7↑:3↓ orpoly(p-hydroxystyrene/styrene/tert-butyl methacrylate) wherein the ratioof p-hydroxystyrene units to the sum of styrene units and tert-butylmethacrylate units is limited to 7↑:3↑.
 31. The resist composition asclaimed in claim 26, wherein the acid generator is a compoundrepresented by the general formula [8], [9], [11], [12], [13] and [15];

wherein R₉ and R₁₀ are independently an alkyl group or a haloalkyl groupand A′ is a sulfonyl group or a carbonyl group;

wherein R₁₁ is a hydrogen atom, a halogen atom, an alkyl group, analkoxy group or a haloalkyl group, and R₁₂ is an alkyl group, ahaloalkyl group or a group shown by the following general formula [10]:

wherein R₁₃ is a hydrogen atom, a halogen atom, an alkyl group, analkoxy group or a haloalkyl group, and q is 0 or an integer of 1 to 3;

wherein R₁₄ is a hydrogen atom, a halogen atom, an alkyl group or atrifluoromethyl group and R₁₅ is an alkyl group, an aralkyl group, analkoxy group, a phenyl group or a tolyl group;

wherein R₁₆ is an alkyl group, a phenyl group, a substituted phenylgroup or an aralkyl group, R₁₇ and R₁₈ are independently a hydrogenatom, an alkyl group, a phenyl group, a substituted phenyl group or anaralkyl group, and R₁₉ is a fluoroalkyl group, a trifluoromethylphenylgroup, a methyl group or tolyl group;

wherein R₂₉ is an alkyl group, a fluoroalkyl group, a phenyl group, asubstituted phenyl group or an aralkyl group, Q′ is a sulfonyl group ora carbonyl group, R₃₀ and R₃₁ are independently a hydrogen atom, amethyl group, a methoxy group, a nitro group, a cyano group, a hydroxygroup or a group shown by the following general formula [14]:

wherein R₃₃ is an alkyl group, a fluoroalkyl group, a phenyl group, asubstituted phenyl group or an aralkyl group, Q′ is a sulfonyl group ora carbonyl group, and R₃₂ is a hydrogen atom, a methyl group or an ethylgroup;

wherein R₃₄ is an alkyl group, a fluoroalkyl group, a phenyl group, asubstituted phenyl group or an aralkyl group, R₃₅ is a hydrogen atom, amethyl group, a fluoroalkyl group, a methoxy group, a nitro group, acyano group, a hydroxy group or a group shown by the above generalformula [14].
 32. The resist composition as claimed in claim 26, whereinthe compound which becomes soluble in an aqueous alkaline developingsolution by a chemical change by action of an acid is an alkalineinsoluble compound in which a part or all of phenolic hydroxy groups inan alkaline soluble compound having phenolic hydroxy groups areprotected by a tert-butoxycarbonyl group, a tert-butyl group, a1-methoxyethyl group, a 1-ethoxyethyl group, a tetrahydropyranyl groupor a 1-methylcyclohexyloxycarbonylmethyl group.
 33. The resistcomposition as claimed in claim 26, wherein the compound which becomessoluble in an aqueous alkaline developing solution by an chemical changeby an action of an acid is includes one shown by the following generalformula [16] or

wherein R₅₁ is an alkyl group, an alkoxycarbonyl group, an alkoxyalkylgroup, a tetrahydrofuranyl group or a tetrahydropyranyl group, s is 1 to3, Y is a divalent or trivalent aliphatic hydrocarbon residue which mayhave a substituent, (R₅₁—O)s means that s numbers (in which s is 2 or 3)of the group (R₅₁—O) are substituted at the benzene ring, and a carbonatom in the hydrocarbon residue of Y and a carbon atom in the groupshown R₅₁ may form together an aliphatic ring.
 34. A resist compositionfor a special substrate being selected from the group consisting of SiN,TiN, SiON, BPSG and a strong basic organic anti-reflective film, whichcomprises; a) a compound selected from the group consisting of methylglycolate, ethyl glycolate, n-propyl glycolate, isopropyl glycolate,n-butyl glycolate, isobutyl glycolate, tert-butyl glycolate, n-pentylglycolate, isopentyl glycolate, n-hexyl glycolate, cyclohexyl glycolate,methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, n-propyl3-hydroxypropionate, methyl 2-hydroxybutyrate, ethyl 2-hydroxybutyrate,n-propyl 2-hydroxybutyrate, methyl 2-hydroxyisobutyrate, ethyl2-hydroxyisobutyrate, methyl 3-hydroxybutyrate, ethyl 3-hydroxybutyrate,methyl 3-hydroxyvalerate, ethyl 3-hydroxyvalerate, methyl mandelate,ethyl mandelate, n-propyl mandelate and isopropyl mandelate, b) apolymer soluble in an aqueous alkaline developing solution, c) an acidgenerator, and d) a cross-linking compound which can make a polymerhardly soluble in an aqueous alkaline developing solution by a chemicalchange by an action of an acid.
 35. The resist composition as claimed inclaim 34, wherein an amount of the compound to be used is 0.5 to 30 wt %relative to the total amount of the resist composition.
 36. The resistcomposition as claimed in claim 34, wherein the compound is methylglycolate, ethyl glycolate, methyl 2-hydroxybutyrate, ethyl2-hydroxybutyrate, methyl 3-hydroxybutyrate, ethyl 3-hydroxybutyrate,methyl mandelate or ethyl mandelate.
 37. The resist composition asclaimed in claim 34, wherein the compound is methyl glycolate, ethylglycolate, methyl 3-hydroxybutyrate, ethyl 3-hydroxybutyrate or ethylmandelate.
 38. The resist composition as claimed in claim 34, whereinthe polymer soluble in an aqueous alkaline developing solution ispoly(p-hydroxystyrene), poly(styrene/p-hydroxystyrene) wherein the ratioof styrene units to p-hydroxystyrene units is limited to 4 or less:6 ormore, said ratio being hereinafter represented by 4↓:6↑,poly(p-tert-butoxystyrene/p-hydroxystyrene) wherein the ratio ofp-tert-butoxystyrene units to p-hydroxystyrene units is limited to2↓:8↑, poly(p-isopropoxystyrene/p-hydroxystyrene) wherein the ratio ofp-isopropoxystyrene units to p-hydroxystyrene units is limited to 2↓:8↑,poly(p-tetrahydropyranyloxystyrene/p-hydroxystyrene) wherein the ratioof p-tetrahydropyranyloxystyrene units to p-hydroxystyrene units islimited to 2↓:8↑, poly(p-tert-butoxycarbonyloxystyrene/p-hydroxystyrene)wherein the ratio of p-tert-butoxycarbonyloxystyrene units top-hydroxystyrene units is limited to 2↓:8↑,poly(p-1-ethoxyethoxystyrene/p-hydroxystyrene) wherein the ratio ofp-1-ethoxyethoxystyrene units to p-hydroxyxtyrene units is limited to2↓:8↑,poly(p-1-ethoxyethoxystyrene/p-tert-butoxystyrene/p-hydroxystyrene)wherein the ratio of the sum of p-1-ethoxyethoxystyrene units andp-tert-butoxystyrene units to p-hydroxystyrene units is limited to2↓:8↑, poly(p-1-ethoxyethoxystyrene/styrene/p-hydroxystyrene) whereinthe ratio of the sum of p-1-ethoxyethoxystyrene units and styrene unitsto p-hydroxystyrene units is limited to 2↓:8↑,poly(p-hydroxystyrene/styrene/tert-butyl acrylate) wherein the ratio ofp-hydroxystyrene units to the sum of styrene units and tert-butylacrylate units is limited to 7↑:3↓ orpoly(p-hydroxystyrene/styrene/tert-butyl methacrylate) wherein the ratioof p-hydroxystyrene units to the sum of styrene units and tert-butylmethacrylate units is limited to 7↑:3↓.
 39. The resist composition asclaimed in claim 34, wherein the acid generator is a compoundrepresented by the general formula [8], [9], [11], [12], [13] and [15];

wherein R₉ and R₁₀ are independently an alkyl group or a haloalkyl groupand A′ is a sulfonyl group or a carbonyl group;

wherein R₁₁ is a hydrogen atom, a halogen atom, an alkyl group, analkoxy group or a haloalkyl group, and R₁₂ is an alkyl group, ahaloalkyl group or a group shown by the following general formula [10]:

wherein R₁₃ is a hydrogen atom, a halogen atom, an alkyl group, analkoxy group or a haloalkyl group, and q is 0 or an integer of 1 to 3;

wherein R₁₄ is a hydrogen atom, a halogen atom, an alkyl group or atrifluoromethyl group and R₁₅ is an alkyl group, an aralkyl group, analkoxy group, a phenyl group or a tolyl group;

wherein R₁₆ is an alkyl group, a phenyl group, a substituted phenylgroup or an aralkyl group, R₁₇ and R₁₈ are independently a hydrogenatom, an alkyl group, a phenyl group, a substituted phenyl group or anaralkyl group, and R₁₉ is a fluoroalkyl group, a trifluoromethylphenylgroup, a methyl group or tolyl group;

wherein R₂₉ is an alkyl group, a fluoroalkyl group, a phenyl group, asubstituted phenyl group or an aralkyl group, Q′ is a sulfonyl group ora carbonyl group, R₃₀ and R₃₁ are independently a hydrogen atom, amethyl group, a methoxy group, a nitro group, a cyano group, a hydroxygroup or a group shown by the following general formula [14]:

wherein R₃₃ is an alkyl group, a fluoroalkyl group, a phenyl group, asubstituted phenyl group or an aralkyl group, Q′ is a sulfonyl group ora carbonyl group, and R₃₂ is a hydrogen atom, a methyl group or an ethylgroup;

wherein R₃₄ is an alkyl group, a fluoroalkyl group, a phenyl group, asubstituted phenyl group or an aralkyl group, R₃₅ is a hydrogen atom, amethyl group, a fluoroalkyl group, a methoxy group, a nitro group, acyano group, a hydroxy group or a group shown by the above generalformula [14].
 40. The resist composition as claimed in claim 34, whereinthe cross-linking compound is one shown by the general formula [4];

wherein R₃₆ is an alkyl group, R₃₇ is a hydrogen atom or a group shownby the general formula [5]:

wherein R₃₆ has the same meaning as above, or one shown by the generalformula [6];

wherein R₃₈ is a hydrogen atom or an alkyl group, and R₃₉ is a hydrogenatom or a group shown by the general formula [7]:

wherein R₃₈ has the same meaning as above.